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REMOVAL OF COPPER ION FROM

WASTE WATER BY FLOTATION

A Thesis

Submitted to the College of Engineering of the University of Baghdad in


Partial Fulfillment of the Requirement for the Degree of Master of Science
in Environmental Engineering

By

Farah Ibrahim Abed Al-Obaidi

(B.Sc. in Water Resource Engineering)



) (
CERTIFICATE OF SUPERVISOR

I certify that this thesis entitled

REMOVAL OF COPPER ION FROM WASTE


WATER BY FLOTATION

Presented by Farah Ibrahim Abed, was prepared under my supervision in the


Environmental Engineering Department of Baghdad University in partial
fulfillment of the requirements for the degree of Master Science in
Environmental Engineering.

Signature:

Ass. Prof. Dr. Ahmed Abed Mohammed

Supervisor

Date: / / 2011

In view of the available recommendation, I forward this thesis for debate by


the Examining Committee.

Signature:

Prof. Dr. Abbas H. Sulaymon

Head of Environmental Engineering Department

Date: / / 2011
CERTIFICATION

We Certify that we have read this thesis and ad an examining committee


examined the student in its content and that in our opinion it meets the
standard of a thesis for the degree of Master of Philosophy in Environmental
Engineering.

Signature Signature

Prof. Abbas H. Sulaymon Ass. Prof. Ayad A. Faisal

(Member) (Member)

Signature Signature

Dr.Khlid Murshed O.A. Ass. Prof. Ahmed A. Mohammed

(Member) (Supervisor)

Approved by University

Signature

Prof. Dr. Qassim Muhammed Doos Al-Attaby

Acting dean, Collage of Engineering

Date: / /2011
To My Parents
Sisters and Brothers
Farah
ACKNOWLEDGMENT

I wish to express my sincere appreciation and utmost gratitude to my


supervisor Ass. Prof. Dr. Ahmed Abed Mohammed for his continuous
guidance and encouragement in directing this work.

Also, I would like to thank the many persons who in one way or another
have participated in the completion of this work; particularly I appreciate the
efforts of: Prof. Dr. Abbas H. Sulaymon the head Environmental
Engineering Department, University of Baghdad for his encouragement and
providing the research facilities and all the staff of Environment Engineering
Department for their help and assistance throughout the research.

I
REMOVAL OF COPPER ION FROM
WASTE WATER BY FLOTATION
By
Farah Ibrahim Abed
Supervised by
Ass. Prof. Dr. Ahmed A. Mohammed
Environmental Engineering Department-College of Engineering
University of Baghdad

Abstract

Several industrial wastewater streams may contain heavy metal ions,


which must be effectively removal before the discharge or reuse of treated
waters could take place.
Various parameters such as pH, air flow rate, collector and frother
concentrations, initial copper concentration, hole diameter of the gas
distributor and NaCl addition were tested at room temperature in a bubble
column of 6 cm inside diameter and 120 cm height.
Sodium dodecylsulfate (SDS) and Hexadecyltrimethyl ammonium bromide
(HTAB) were used as anionic and cationic surfactant, respectively. Ethanol
was used as frothers and the optimal removal conditions have been
established. Successful removals about (98%) and (76%) could be achieved
for copper ions with SDS and HTAB, respectively. Copper removal reached
about 80% under the optimum conditions at low pH; at high pH it became as
high as 98% probably due to the contribution from the flotation of
precipitated copper.

II
Abstract

It was found that the presence of NaCl in the solution reduced the
recoveries since the presence of excess Na+ ions compete with metal and the
metal ions cannot find enough surfactant molecules to attach to. Adding
ethanol at 1% concentration increased the removal efficiency. From the
results the rate of flotation was found to be first order.

III
CONTENTS

Acknowledgment .................................................................................................... I
Abstract .....................................................................................................II
Contents ................................................................................................... IV
List of Figures..VI
List of Tables... VIII
Nomenclature ............................................................................................ X
Chapter One Introduction ......................................................................1
1.1 Statement of Pollution Problem ..............................................................1

1.2 Harmful Effects of Heavy Metals ...........................................................3

1.3 Scope of the Study .................................................................................4

Chapter Two Literature Survey...5


2.1 Common Methods Used to Remove Heavy Metals ................................5
2.1.1 Chemical Precipitation ..................................................................5

2.1.2 CoagulationFlocculation ..............................................................6

2.1.3 Ion Exchange ................................................................................6

2.1.4 Reverse Osmosis ...........................................................................7

2.1.5 Electrodialysis ...............................................................................7

2.1.6 Adsorption .....................................................................................8

2.2 Flotation .................................................................................................8


2.3 Metal ions ............................................................................................ 12

2.4 Surfactant ............................................................................................. 13

2.5 Frother ................................................................................................. 16

2.6 Air bubbles .......................................................................................... 20


2.7 Gas sparger .......................................................................................... 21
IV
Contents

2.8 Foam or Froths ..................................................................................... 22

2.9 Modifiers ........................................................................................... 26

2.10 pH of the system ................................................................................ 26

2.11 Flotation kinetics ................................................................................ 27

2.12 Previous related research .................................................................... 28

Chapter Three Experimental Work ..................................................... 35


3.1 Materials .............................................................................................. 35
3.1.1 Reagents ..................................................................................... 35
3.1.2 Gas ............................................................................................. 36
3.2 General Description and Procedure ...................................................... 36
3.2.1 General Description .................................................................... 36
3.2.2 Preparation of solution ............................................................... 36
Chapter Four Results and Discussion ................................................... 39
4.1 Effect of pH ......................................................................................... 39
4.2 Effect of surfactant type ...................................................................... 41
4.3Effect of initial copper concentration .................................................... 42

4.4Effect of surfactant concentration .......................................................... 45

4.5 Effect of air flow rates ........................................................................ 48

4.6 Effect of frothers ................................................................................. 51

4.7 Effect of ionic strength ......................................................................... 53

Chapter Five Conclusions and Recommendations ............................... 56


5.1 Conclusions .......................................................................................... 56

5.2 Recommendations ................................................................................ 58

References ................................................................................................ 59
Appendix .................................................................................................. 71
V
List of Figures
Figure 2.1 Typical ion flotation process. 10

Figure 2.2 speciation diagrams for the Cu (II)H2O system... 13

Figure 2.3 Schematic diagram of the effect of the frother Concentration


upon bubble size in a flotation cell..17

Figure 2.4 flow chart showing how ion flotation with dodecyl sulfate and
electrolytic metal recovery could be used to remove residual metal ions
from a process effluent.25
Figure 3.1Schematic diagram of the experimental set-up...38

Figure 3.2 Experimental set-up of the flotation column used in the present
study .38

Figure 4.1 Effect of pH on the removal ratio of copper ions..40

Figure 4.2 Rate constant at various pH40

Figure 4.3 Effect of surfactant type on the removal ratio of copper(Co=100


mg/l; Q=250ml/min; SDS=75mg/l; HTAB=75mg/l; ethanol = 1 % ,
do =1 mm)41

Figure 4.4 Effect of surfactant concentration on the removal rate of copper


(pH=10; Co=100 mg/l; Q=250 ml/min; ethanol=1%;do=1mm)...44

Figure 4.5 Effect of surfactant concentration on the removal rate of copper


(pH=4; Co=25 mg/l; Q=250 ml/min; ethanol=1%,do=1mm). .44
Figure 4.6 ln (C/Co) versus time at different SDS concentration. (pH=10;
Co=100 mg/l; Q=250 ml/min; ethanol=1%,do=1mm)..45

Figure 4.7 Effect of copper concentration on the removal rate (pH=10; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm).47

VI
Figures

Figure 4.8 Effect of copper concentration on the removal rate (pH=4; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm)47

Figure 4.9 Effect of gas flow rate on the removal rate of copper (pH=4;
Co=25 mg/l; SDS=350 mg/l; ethanol=1%,do=1mm)49

Figure 4.10 Effect of gas flow rate on the removal rate of copper (pH=10;
Co=100 mg / l; SDS=75 mg/l; ethanol=1%,do=1mm).49

Figure 4.11 Effect of hole diameter of the gas distributor on the removal
rate of copper(pH=4;Co=25mg/l;SDS=350mg/l; Q=250ml/min; ethanol = 1
% )..51

Figure 4.12 Effect of ethanol concentration on the removal rate of copper


(pH=4; Co=25 mg/l; SDS=350 mg/l; Q=250 ml/min, do=1mm)52

Figure 4.13 Effect of ethanol concentration on the removal rate of copper


(pH=10; Co =100 mg/l; SDS=75 mg/l; Q =250 ml/min, do=1mm). 53

Figure 4.14 Effect of NaCl concentration on the removal rate of copper


(pH=4; Co=25 mg/l; SDS=350 mg/l; Q=500 ml/min; ethanol = 1% ,
do=1mm).54

Figure 4.15 Effect of NaCl concentration on the removal rate of copper


(pH=10; Co =100 mg/l; SDS=75 mg/l; Q =250 ml/min; ethanol = 1 % ,
do=1mm)................................55

VII
List of Tables
Table 1.1Copper levels reported in industrial waste waters .3

Table1.2 EPA regulations for industrial effluents pollution of surface


waters..3

Table 1.3 Health effects of heavy metals4

Table 3.1.Selected Properties of Surfactants Used in This Study.35


Table 4.1 Rate constants at various pH.........41

Table 4.2 Rate constant at various SDS concentrations.45

Table 4.3 Rate constant at various initial copper concentrations...48

Table 4.4 Rate constants at various gas flow rate..50

Table 4.5 Rate constants at various ethanol concentrations..53

Table 4.5 Rate constants at various NaCl concentrations...55

Table 5 Residual Copper Concentration at Different pH, Co = 100 mg/l;


SDS=75mg/l, HTAB=75mg/l, Q=250ml/min, Ethanol=1, do=1mm.71

Table 6 Effect of Initial Copper Concentration on the Removal Rate, pH=10,


Q=250 ml/min, SDS=75 mg/l, Ethanol=1%, do=1mm72

Table 7 Effect of Initial Copper Concentration on the Removal Rate, pH=4,


Q=250 ml/min, SDS=75 mg/l, Ethanol=1%, do=1mm.72

Table 8 C/Co at Various Concentration of SDS, pH=10, Q=250 ml/min, Co


=100 mg/l, Ethanol=1%, do=1mm..73

Table 9 C/Co at Various Concentration of SDS, pH=4, Q=250 ml/min, C o


=25 mg/l, Ethanol=1%, do=1mm73

Table 10 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=10,
Co =100 mg/l, SDS=75 mg/l, Ethanol=1%, do=1mm..74
VIII
Tables

Table 11 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=4, Co
=25 mg/l, SDS=350 mg/l, Ethanol=1%, do=1mm74

Table 12 C/Co at Various Ethanol Concentration, pH=10, Co=100 mg/l, SDS


=75 mg/l, Q =250 ml/min, do=1mm75

Table 13 C/Co at Various Ethanol Concentration, pH=4, Co=25 mg/l, SDS


=350 mg/l, Q=250 ml/min, do=1mm..75

Table14 Effect of NaCl Concentration on the Removal Rate of Copper, pH


=10, Co=100 mg/l, SDS=75 mg/l, Q =250 ml/min. Ethanol=1%,
do=1mm.76

Table15 Effect of NaCl Concentration on the Removal Rate of Copper,


pH=4, Co=25 mg/l, SDS=350 mg/l, Q=500 ml/min, Ethanol=1%,
do=1mm.76

Table 16 Effect of hole diameter of the gas distributor on the removal rate of
copper, pH=4, Co=25 mg/l, SDS=350 mg/l, Q=250 ml/min,
Ethanol=1%...................................................................................................77

IX
NOMENCLATURE

Symbol Units
Co Initial copper concentration mg/l
C Residual copper concentration mg/l
CMC Carboxymethyl cellulose -
db Bubble diameter m
do Hole diameter mm
DAF Dissolved air flotation -
g Acceleration due to gravity m/s2
H Bed height m
HDS High dodecyl sulfate -
HTAB Hexadecyltrimethyl ammonium bromide -
IAF Induced air flotation -
k Rate constant min-1
n order of flotation equation -
Q Gas flow rate ml/min
R Recovery -
Sb bubble surface area cm2
SDS Sodium dodecylsulfate -
ug Interstitial gas velocity m/s

Creek symbols Units

Liquid viscosity Kg/m.


Surface s
tension N/m
Liquid density Kg/m3
X

Chapter One
INTRODUCTTON

1.1 Statement of Pollution Problem


Water pollution is nowadays a matter of deep apprehension. Many
industrial wastewaters contain numerous toxic metals, such as chromium,
mercury, cadmium, lead, copper, which must be removed before reuse of the
water or its discharge to the environment. According to environmental
regulations , there is an increasing concern about the removal of metal in the
effluent streams. Therefore, the scientific research is being directed towards
the implementation of novel approaches dealing with the efficient removal
of toxic metals from waste water (Zhang et al., 2009).
The wastewater treatments used for removal of toxic metals include the
convention a physicochemical treatment of addition of inorganic coagulants
and polymers, subsequent precipitation, aeration, and final neutralization.
However, the final step, which should involve the treatment and safe
disposal of toxic sludge, has been largely ignored (Matis et al., 2001).
In the treated industrial wastewaters, depending on reuse/recycling
options; some of the values often exceed legal limits. Therefore, the
necessity of innovative, simple, and economical treatment methods for the
final polishing step or tertiary treatment are needed (Matis et al., 2001).
Heavy metals are metals with densities generally larger than 5 g/cm3.
It can have serious effects on human and animal health. Beside the health
effects, heavy metals are nonrenewable resources. Therefore, effective
recovery of heavy metals is as important as their removal from waste
streams (Badmus et al., 2007).

Chapter One
Introduction

The toxicity of heavy metals can be listed in order of decreasing toxicity


as Hg > Cd > Cu > Zn > Ni > Pb > Cr >Al >Co, although this is only
approximate as the vulnerability of species to individual metals varies.
Toxicity also varies according to environmental conditions that control the
chemical speciation of the metals (Gray, 2005).Among these metals copper
will be studied in this thesis.
Copper has received considerable attention owing to its uses in
metallurgy, chemical industries and is necessary for other many biological
important functions. When levels of Cu exceed certain values, however,
defense mechanisms to protect against excess Cu are overcome and toxicity
results. The reported list of toxic Cu species includes CuOH+, Cu2OH2+2 and
CuCO3.However, without doubt,Cu+2 ions that are present in various
aqueous solutions (their presence is a function of pH) are considered to be
the most toxic of dissolved copper species (Khalifa et al., 2001).Excess
copper in water is not only harmful to human beings, but also interferes with
the self-purification of bulk water (Ghazy et al., 2006) and adverse effect on
the microbiological treatment of wastewater (Ghazy et al., 2008).
As the industries advance, copper has been come one of the most widely
used metals. The primary sources of copper in industrial wastewaters are
metal process pickling baths and plating baths (Eckenfelder et al.
2009).Copper may also be present in wastewaters from a variety of chemical
manufacturing processes employing copper salts or a copper catalyst in
different range from o.12 mg/l to 183 mg/l such as mining acid, mine
drainage, paint and pigment manufacturing and motor vehicle (Table 1.1).
In order to reduce the pollution problem in environment that is caused by
these heavy metals, their concentration must be reduced before discharging
to obey the wastewater standards listed in Table 1.2.So an effective
treatment process must be applied.

Chapter One
Introduction

Table 1.1Copper levels reported in industrial wastewaters


(Metcalf and Eddy, 2003)

Industrial source Copper Concentration(mg/l)


Paint and pigment manufacturing 0.04-100
Motor vehicle and aircraft plating 0.5-33
Copper plating baths 2.2-183
Petroleum Refining 0.0-1.4
Copper ore extraction 0.28-20
Acid mine drainage 0.12-128

Table 1.2 EPA regulations for industrial effluents pollution of surface waters
(Misra, 1995)

Substances Limits(mg/l)

Copper 1

Sliver 0.2-2g/l

Chromium 0.5

Zinc 5
1.2 Harmful Effects of Heavy Metals
Industrial activity is the main culprit behind most environmental
pollution problems and ecosystem damage, coming from the accumulation
of pollutants such as toxic metals chromium, copper, lead, cadmium, zinc,
etc. (Pino et al., 2006).Contamination of soils, groundwater, surface water
Chapter One
Introduction

and air with hazardous and toxic chemicals poses significant problems for
both human health and the environment (Ansari et al., 2007). In view of the
human health impacts, each metal imparts different effects and symptoms.
For example, copper is an essential element but can cause adverse health
effects. The safe and adequate copper intake is 1.5 to 3 mg/day (National
Research Council, 1989); however, at high doses, copper can cause acute
effects, such as astrointestinal (GI) disturbances, damage to the liver and
renal systems, and anemia. (Letterman et al., 1999).Health effects of Cu, Pb,
Cd and Ni were given in Table 1.3.

Table 1.3 Health effects of heavy metals


(Kurniawan et al., 2006)
Heavy Metal Toxicities
Cu(II) Liver Damage, Wilson disease, insomnia.

Pb(II) Depression, lethargy, neurologic signs, increased thirst.

Cd(II) Kidney damage, renal disorder, Itai-Itai, probable carcinogen.

Ni(II) Dermatitis, nausea, chronic asthma, coughing.

1.3 Objective of the Study


In present work , the flotation of copper in wastewater had been studied
in a batch flotation cell with air bubbles being generated by a dispersion
mechanism. The effects of various variables on the separation efficiency at
room temperature such as gas flow rate, copper concentration , surfactants
types and concentrations ,pH range , ethanol concentrations , ionic strength
and the effect of different size of hole distributer has been studied.
Chapter Tw0
LITERATURE SURVEY

2.1 Common Methods Used to Remove Heavy Metals from


Industrial Wastewaters
There are various methods for removing metals from water and
wastewater, e.g., chemical precipitation, ion exchange, reverses osmosis.
These methods are relatively expensive, involving either costly equipment or
elaborate procedures, and with some techniques, large volumes of secondary
wastes are generated (Sabti et al., 2002).The summary of these methods will
be given in the following paragraphs.

2.1.1 Chemical Precipitation


Chemical precipitation is most commonly employed for most of the
metals. When properly monitored and controlled, chemical precipitation is a
very effective means of metal removal in many waste streams. It currently is
by far the most cost-effective means of reducing metal concentration to meet
local environmental regulations .In general, chemical precipitation works
best on more concentrated metal solutions. Low concentration solutions (50
to 250 mg/L) are very difficult to treat, as contact between the metal and
precipitating chemical is greatly reduced (Flynn, 2009).
Common precipitants include OH-, CO3-3 and S-2 Metals are precipitated
as the hydroxide through the addition of lime or caustic to a pH of minimum
solubility (Eckenfelder et al., 2009).
Chemical precipitation requires a large amount of chemicals to reduce
metals to an acceptable level for discharge (Galla et al., 2000).
Other drawbacks are its excessive sludge production that requires further
Chapter One
Introduction

treatment, the increasing cost of sludge disposal, slow metal precipitation,


poor settling, the aggregation of metal precipitates, and the long-term
environmental impacts of sludge disposal (Yang et al., 2001; Bose et al.,
2002; Wingnfelder et al., 2005). In addition, the residual concentrations are
not always as low as desired (Jamaleddin et al, 2000).

2.1.2 CoagulationFlocculation
Coagulationflocculation can be employed to treat wastewater laden with
heavy metals. Principally; the coagulation process destabilizes colloidal
particles by adding a coagulant and results in sedimentation (Shammas et al.,
2004).To increase the particle size, coagulation is followed by the
flocculation of the unstable particles into bulky floccules (Semerjian
and Ayoub, 2003).In spite of its advantages, coagulationflocculation has
Limitations such as high operational cost due to chemical consumption. The
increased volume of sludge generated from coagulationflocculation may
hinder its adoption as a global strategy for wastewater treatment. This can be
attributed to the fact that the toxic sludge must be converted into a stabilized
product to prevent heavy metals from leaking into the environment. To
overcome such problems, electro-coagulation may be a better alternative
than the conventional coagulation, as it can remove the smallest colloidal
particles and produce just a small amount of sludge. However, this technique
also creates a floc of metallic hydroxides, which requires further
purification, making the recovery of valuable heavy metals impossible
(Ayoub et al., 2001).

2.1.3 Ion Exchange


Another method used for removal of heavy metals is ion exchange. Ion
exchange is used widely in the metal finishing industry to remove dissolved

Chapter One
Introduction

heavy metals from the rinse water such as for the removal of nickel, copper,
tin, aluminum anodizing and zinc ions (Seneviratne, 2006).
It is a reversible chemical reaction where ions in a feed stream are
exchanged for similarly charged ions on the surface of a solid ion exchange
resin. Once capacity of the resin is reached (most ions of the resin are
exchanged), the resin is taken out of service for regeneration. The
performance and economics of ion exchange are related to the capacity of
resin (Eckenfelder, 2009).

2.1.4 Reverse Osmosis


Reverse osmosis is the most widely used membrane filtration process in
treatment of waste and raw water. The effective size range for RO makes the
technique applicable for removal of atomic sized species. In fact, reverse
osmosis has the capability of retaining 99% of multivalent ions and about
95% of monovalent ions in the concentrated stream. This technique is most
applicable for concentrating a heavy metal for recycling, or coupling with
other methods such as electrolytic recovery or evaporation to recover the
metal (Flynn, 2009).

2.1.5 Electrodialysis
In the electrodialysis process, ionic components of a solution are
separated through the use of semi permeable ion-selective membranes. This
process may be operated in either a continuous or a batch mode. Among the
technical problems associated with the electrodialysis process, concentration
polarization is perhaps the most serious. Other problems in practical
applications include membrane scaling by inorganic in feed solutions as well
as membrane fouling by organics (Nicholas, 2002).

Chapter One
Introduction

2.1.6 Adsorption
Adsorption is a physical process where soluble molecules (adsorbate) are
removed by attachment to the surface of a solid substrate (absorbent)
primarily by Vander Waals forces, although chemical or electrical attraction
may also be important. Adsorbents must have a very high specific surface
area and include activated alumina, clay colloids, hydroxides and adsorbent
resins, with the most widely used being activated carbon. Activated carbon
can be very effective in removing metal ions from wastewater by first
chelating the metal ions with an organic chelant, such as citric acid or
EDTA. When the chelated mixture treated using activated carbon, the
organic chelant will adsorb to the carbon, removing the chelated metals
along with it (Woodard, 2006). Although, adsorption has been well
established as a technology for removing toxic compounds from wastes or
wastewaters (Zouboulis et al., 1994), the process may face filter-blocking
problems (Ghazy et al., 2008).

2.2 Flotation
Flotation as a separation process has recently received a considerable
interest owing to its simplicity, rapidity, economy, good separation yields
(Recovery> 95 % for small impurity agent concentrations (10-610-2 mol.L-1)
,a large possibility of application for species having different nature and
structure, flexibility and friability of equipment and processing for recovery
purpose and production of more concentrated sludge, occupying smaller
volumes(Matis, 1995; Stoica et al., 1998; Voronin and Dibrov, 1999;
Pacheco and Torem, 2002; Rubio et al., 2002; Matis et al., 2004; Medina
et al., 2005; Rosa and Rubio, 2005; Carissimi and Rubio, 2005). It is
believed that this process will be soon incorporated as a clean technology to

Chapter One
Introduction

treat water and wastewater (Ghazy et al., 2008). Therefore, flotation


technique was selected for this investigation.
Foam separation is generally used in separation and concentrating soluble
materials from aqueous solution. When dealing with dilute wastes, foam
separation has several advantages: low residual metal concentration,
rapid operation, low space requirements, and low cost (Carleson et al., 1989;
Nicol et al., 1992; Choi et al., 1998; Watcharasing et al., 2009; Shakir et al.,
2010). However, it is still uncommon in hydrometallurgy and with the
purification of waste waters. This is primarily associated with the difficulties
in the regeneration of reagent collectors (Abryutin et al., 2010).
Among the methods of foam separation, ion and precipitate flotation
usually implies the removal of metal ions from aqueous solutions. Ion
flotation involves the removal of surface inactive ions from aqueous
solutions by the introduction of a surfactant and the subsequent passage of
gas bubbles through the solution. The surfactant molecules automatically
position themselves on the bubble surfaces, with their polar functional
groups facing the bulk solution. Certain non-surface-active counter ions in
the solution, also called colligends (e.g., metal ions), and may also attach to
the bubble surfaces, by either electrostatic or chemical interactions with the
surfactant functional groups. When the bubbles emerge from the solution,
they should form a stable foam phase. The collector and colligend adsorbed
onto the bubbles report to the foam and can be physically separated from the
solution (Liu et al., 2009). Higher concentrations of floated ions and
surfactant may lead to precipitation of sublate in the solution. Ion flotation
carried out under these conditions is a form of precipitate flotation
(Zouboulis et al., 1987). Figure 2.1 shows a typical ion flotation process.

Chapter Two
Literature Survey

Figure 2.1 Typical ion flotation process


(Liu et al., 2009)

Air flotation has been applied to the separation of heavy metal from water
; the operation may be classified in to: (1) Dissolved air flotation, and (2)
Induced air flotation with respect to the generation of fine bubbles. In
IAF(Induced air flotation )bubbles are generated by passing the gas through
some kind of disperser: porous media, perforated tubes (spargers), impeller,
etc. Bubble diameter is in order of 1000m.In DAF bubbles are produced
when the pressure of super saturated solution is lowered to atmospheric
pressure and this is done by saturating the liquid at high pressure and
releasing the pressure. Bubble sizes are small, ranging from 30 t0 120 m
(Lawrence et al., 2010).

Chapter Two
Literature Survey

Induced air flotation has low retention times while dissolved air flotation
are higher (20-60min).So that, dissolved air flotation is inefficient when the
treatment of high volumes effluents and high flow rates is required
(Mohammed , 2004).
In general, the DAF process can provide the highest treatment efficiency.
However, DAF process has some limitations in terms of investment
cost, complex operations and equipment size (Painmanakul et al., 2010).
Therefore, IAF process is an attractive alternative and chosen for this study.
Column flotation is still a subject of great interest in mineral processing
with a steadily growing number of research studies and industrial
applications (Rubinstein, 1994; Finch, 1995). Applications of column
flotation in the field of recovery of heavy metals (Filippov and Filippova,
2003) have been reported.
Some of the advantages claimed with flotation columns include
improved separation performance, particularly for fine materials; low
capital and operating costs; low plant floor space requirements;
and easy adaptability to automatic control. Flotation columns are being
used in iron ore, copper, lead, zinc, chromium, cadmium, and coal
flotation applications and are expected to become even more popular
because their simplicity in construction and flexibility of operation (Perry et
al., 1997).
Chapter Two
Literature Survey

2.3 Metal ions


When a soluble metal salt is added to water it will dissociate and the ions
will become hydrated. In addition, if the metal is capable of undergoing
hydrolysis it will also react with water thereby lowering the pH and forming
mononuclear and perhaps polynuclear hydroxo species in a stepwise series.
The exact distribution of the various species formed , and indeed their nature,
will depend primarily on the solution pH, and to a lesser extent on the
temperature and the type and concentration of solution components as well
as other physical and chemical characteristics of the system.It would be
expected then that varying the hydrogen ion concentration of a solution of
such a metal would have a profound effect on its removal by foam
separation (Lemlich, 1972).
Polat and Erdogan (2007) studied the thermodynamic distributions of the
Cu (II) in aqueous solutions as a function of pH. They founded that the
dominant species for copper are the positively chargedCu+2 , CuOH+ and at
pH values less than 10 whereas they are negatively charged Cu(OH)-3 and
Cu(OH)4-2 at pH values greater than10. At and around pH 10, precipitation
of neutral Cu(OH)2 takes place. Fig 2.2.Shows the speciation diagram for the
Cu (II)H 2O system. It is apparent that the pH of the solution is extremely
important in flotation since it dictates the type and the charge of the species
present in solution and therefore the structure of the surfactant (an anionic or
a cationic collector) to be employed.

Chapter Two
Literature Survey

Figure 2.2 speciation diagrams for the Cu (II)H2O system


(Doyle et al., 2003)

2.4 Surfactant
A surfactant (a contraction of the term surface-active agent) is a substance
that, when present at low concentration in a system, has the property of
adsorbing in to the surface or interfaces of the system and altering to a
marked degree the surface or interface free energies of those surfaces (or
interface).The term interface indicates a boundary between any two
immiscible phases; the term surface denotes an interface where one phase is
a gas, usually air (Rosen, 1989).
Surface-active agents have a characteristic molecular structure consisting
of a structural group that has very little attraction for the solvent, known as
a lyophobic group, together with a group that has strong attraction for the
solvent ,called the lyophilic group. This is known as amphipathic structure.
When a surface-active agent is dissolved in a solvent ,the presence of the
lyophobic group in the interior of the solvent may caused distortion in the
interior of the solvent liquid structure, increasing the free energy of the

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system when it is dissolved, means that less work is needed to bring


molecules to the surface, the presence of surfactant decreases the work
needed to create unit area of surface (the surface free energy per unit area, or
surface tension).On the other hand, the presence of the lyophilic
(hydrophilic) group prevents the surfactant from being expelled completely
from the solvent as a separate phase, since that require dehydration of the
hydrophilic group.
The amphipathic structure of the surfactant therefore causes not only
concentration of the surfactant at the surface and reduction of the surface
tension of the water, but also orientation of the molecule at the surface with
its hydrophilic group in the aqueous phase and its hydrophobic group
oriented away from it(Rosen, 1989).
The hydrophobic group is usually along-chain hydrocarbon residue, and
less often a halogenated or oxygenated hydrocarbon or siloxane chain; the
hydrophilic group is an ionic or highly polar group. Depending on the nature
of the hydrophilic group, surfactants are classified as:
1. Anionic. The surface-active portion of the molecule bears a negative
charge.
2. Cationic. The surface-active portion of the molecule bears a positive
charge.
3. Zwitterionic. Positive and negative charges may be present in the
surface-active portion.
4. Nonionic. The surface active portion bears no apparent ionic charge.
The presence of the surfactant can retard the bubble coalescence, owing
to the repulsive force between the adsorbed surfactant layers of air bubbles.
Consequently, the bubble size decreases with an increase in the surfactant
dosage. This is because the surfactant adsorption on the air bubble
surface reduces the surface tension at the air-water interface, which would

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consequently reduce the holding forces during bubble formation, as well as


decreases the coalescence rate of the air bubbles (Watcharasing et al., 2009).
The anionic surfactant, with its negative-charged part, adsorbs on to the
ions while its hydrocarbon chain amplifies hydrophobic character of the
precipitate. As a result of that interaction the gas bubbles passing through the
system attached very well on to the hydrocarbon chain and the separation of
the ions from the liquid phase (Matis et al., 1995).
Increase in the length of the hydrophobic group decreases the solubility of
the surfactant in water and increase its solubility in organic solvent, causes
closer packing of the surfactant molecules at the interface (provided that the
area occupied by the hydrophilic group at the interface permits it), increases
the tendency of the surfactant to adsorb at an interface or to form micelles.
The surface tension of a solution of surfactant decreases steadily as the bulk
concentration of surfactant is increased until the concentration reaches a
value concentration (CMC), above which the tension remains virtually
unchanged. The surface tension at the CMC is therefore very close to the
minimum tension that the system can achieve. The lowest surfactant
concentration at which micelle formation occurs is called critical micelle
concentration (Rosen, 1989).
The micelles formed at the critical micelle concentration are spherical.
Their outside surface is hydrophilic, and the hydrocarbon radicals
constituting the core of the micelle form anon polar medium. When the
surfactant concentration in water is more than ten times higher than CMC,
the spherical micelles, as a rule, are transformed in to cylindrical ones and
the solubility further increases. The lower the C.M.C, the more efficient the
surfactant is to adsorb in to surfaces (lyklema et al., 2004).
Foam height generally increase with increase in surfactant concentration
below the critical micelle concentration until the neighborhood of CMC is

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reached ,in which region foam height reaches a maximum value or increases
slowly to a maximum value somewhat above the CMC. Thus, the CMC of a
surfactant is a good measure of its Efficiency as a foaming agent; the lower
the CMC, the more efficient the surfactant as a foamer. Those structural
factors that produce a lower critical micelle concentration for example,
increased length of the hydrophobic group-would therefore be expected to
increase the efficiency of the surfactant as a foaming agent (Rosen, 1989).
Those surfactants that are suitable for laboratory separation processes are
not necessarily appropriate for large-scale use, particularly environmental
applications, for example, they may be toxic, hazardous, and deleterious to
wildlife, chemically unstable or too expensive (Medina et al. 2005).
The types of ion separations that would be needed in a commercial
hydrometallurgical process differ from those typically encountered in the
laboratory. From an economic perspective, it will be essential that a metal
product can be removed from the foam with regeneration of the collector
(Doyle et al., 2003).
Focusing on surfactants that are likely to be acceptable, several anionic
surfactants with C12 alkyl chains have been used successfully for foam
flotation (Sreenivasarao and Doyle, 1997).

2.5 Frother
Frothers are heteropolar surface-active compounds containing a polar
group (OH, COOH, C=O, OSO2 and SO2 OH) and a hydrocarbon radical,
capable of adsorbing in the air-water interface. The frother molecules are
arranged at the airwater interface such that the hydrophilic or polar groups
are oriented into the water phase and the hydrophobic hydrocarbon chain in
the air phase. In fact, the frother creates conditions for froth formation. The
frother concentrates at the interface of water and air

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bubbles forming an envelope around the bubbles, which prevents them from
colliding or touching (Bulatovic, 2007).
Frothers also lower the surface tension of the water due to heteropolar
nature of the reagent molecules Thus, the surface tension of a solution is an
indication of the activity of frother. Frothers that strongly lower the surface
tension produce more stable froths (Gupta et al., 2007).
The effect of frothers on bubble size has recently been extensively studied
(Cho and Laskowski, 2002; Laskowski et al., 2003; Grau et al., 2005; Gupta
et al., 2007; Melo et al., 2007; Nguyen et al., 2006; Comley et al., 2002). It
was found that the effect of frothers on bubble size results from their ability
to prevent bubble coalescence. As shown schematically in Fig. 2.3, with
increasing frother concentration, the degree of bubble coalescence decreases
and at a particular concentration (critical coalescence concentration, CCC),
the coalescence of the bubbles is completely prevented.
Figure 2.3 Schematic diagram of the effect of the frother concentration upon
bubble size in a flotation cell (Grau et al., 2005)

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The CCC values are obtained by finding the intersection of the horizontal
asymptote to the bubble sizeconcentration curves at higher concentrations
with the sloped line approximating the curve at lower concentrations.
Further increase of the frother concentration above the CCC value does not
affect the bubble size (Grau et al., 2005).
Apart from the ability of frothers to form froth, they have other important
roles including (Bulatovic et al., 2007):
Creating finer bubbles, whereby the dispersion of air in the flotation cell
also improves.
Reducing coalescence of individual air bubbles.
Reducing the rate of bubble rise from the mixing zone to the froth zone.
Increasing the strength of the bubbles and stability of froth.
This may result from two interrelated actions: (a) improvement in air
dispersion and (b) deterioration in the coalescence of air bubbles in the pulp.
Both actions affect froth formation and bubble transport to the froth zone.
Molecules of the frother usually adsorb on air bubbles, thus increasing the
stability of the hydrated layer surrounding the bubble. The hydrophilic
groups of adsorbed frothers are directed to the liquid phase and actively
interact with molecules of water. This in fact leads to an increase in the
mechanical strength of the envelope surrounding the bubbles and prevents
destruction or collision with other bubbles (Bulatovic et al., 2007).
Experimental work carried out by Frumkin et al. (1947) demonstrated
that molecules of surface-active agents, which adsorb on the surface of
bubbles, are shifted to the bottom portion of the air bubble during their
upward movement in the liquid or pulp. This results in lowering the surface
tension in this region, creating difference in the surface tension between the
upper and lower region of the bubble. Along the surface of the air bubble, a

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force is created which attempts to equalize the surface tension to prevent


further shifting of frother molecules to the lower portion of the bubble.
These forces hinder the motion of the molecules on the surface of the air
bubbles, thus lowering the mobility of bubbles. This decrease in mobility
makes the bubbles behave like solid spheres. The decrease in the velocity of
the air bubble due to the surface-active agent is pronounced.The increased
coverage of the lower surface of the bubble is proportional to the amount of
frother concentration in the pulp. It also depends on the size of the air
bubbles, increasing significantly for larger bubbles (Bulatovic et al., 2007).
The science underlying frother selection and design is not clearly
understood. There are general guidelines for this purpose (Mishra et al.,
2007):
The stability of the froth formed must be such that a further degree of
separation of the valuable mineral from the non floatable (entrained)
components is achieved in the froth.
Once the froth containing the valuable component is removed, it must
break readily for further treatment.
The frother must assist formation of a froth of sufficient volume and
stability at low concentrations.
Frother must not have collecting power for gangue minerals.
It must possess a low sensitivity to changes in pH and dissolved salt
concentrations.
It should be relatively inexpensive and abundant for large-scale use.
It must be readily dispersible.
Sulaymon and Mohammed (2010) studied the effect of addition alcohol
on bubble diameter on emulsified oil removal by flotation column, they
concluded that bubble diameter decreased with increased the concentration
of alcohol and this is due to addition of alcohol to the water which acts as a

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surfactant hindering bubble coalescence by accumulating at the air-water


interface, orienting their hydrophilic group in to the liquid film surrounding
the sir bubble. This is creates repulsive electric force when two bubbles
come close to each other.

2.6 Air bubbles


Bubble in flotation machine should be considered as the air phase, whose
sole purpose is to provide air bubbles on which hydrophobic minerals are
attached and transported to the froth phase. Several researches on flotation,
its modification and applications of various types of flotation: Induced Air
flotation and Dissolved Air Flotation and also various advanced techniques
have been considered (Painmanakul et al., 2010).
Recently, Laplante et al. (1983) studied the effect of airflow rate on the
kinetics of flotation. They concluded that when the airflow rate increases,
the size of the air bubble increases, resulting in a decrease in floatability.
Ahmed and Jameson (1985) assumed that the removal of particles
can be described by a first-order rate equation. They found that bubble size
has a strong influence on the flotation rate constant (k).
Zouboulis et al. (1990) studied the effect of air flow rate on foam
Flotation process; they concluded that with the low gas flow rate less
than (2 cm3.S-1) higher retention times (up to 1 hr) were needed. On the
other hand, high gas flow rates higher than (5 cm3.S-1) results usually in the
formation of large amounts of wet foam, indicating a volume of entrained
water, which is difficult to be handled.
Luttrell et al. (1993) derived that the carrying capacity was directly
related to Sb which subsequent experimental work has supported (Li,
1999).The studies conducted by Gorain et al. (1996) on the industrial 2.8m3
flotation cell fitted with different impellers concluded that neither airflow

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rate nor the type of impeller used can be related to floatability. Instead, it is
the bubble surface area flux Sb in the cell that is well correlated with the rate
of flotation.
Hardie et al.(1999) using column flotation for de-inking of recycled paper
showed that ink recovery was well correlated with bubble surface area flux.
Changunda et al. (2008) studies the effect of bubble size on the
flotation rate constant, they concluded that the flotation rate constant
increases approximately linearly with increasing particle size and follows an
inverse power relationship with the bubble size. This inverse power
relationship is due to the increased probability of collision for smaller
bubbles.The collisions between the hydrophobic particles and air bubbles
result in attachment to form bubble-mineral aggregates. Hydrophilic
particles do not attach to the air bubbles, remaining suspended in the water.
The air bubbles carry the attached particles to the surface of the cell forming
a froth zone.
Generally, both of these parameters ,gas flow rate and bubble size, have
been found to influence significantly the rate of the removal (Kinetic effect)
hence the retention time of the metals in the flotation cells and not
particularly the maximum removal using this effect, it has been found to be
possible the selective separation of different metals ions.

2.7 Gas sparger


Gas sparger type is an important parameter that can alter bubble
characteristics which in turn affects gas hold up values and thus many other
parameters characterizing bubble columns. The sparger used definitely
determines the bubble sizes observed in the column. Small orifice diameter
plates enable the formation of smaller sized bubbles. Some common gas
sparger types that are used in literature studies are perforated plate, porous
plate, membrane, and ring type distributors (kantarci et al., 2005).

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Matis et al. (1998) studied the effect of air flow rate on germanium ion
flotation by dispersed-air, involved the use of different fritted glasses in
the flotation cell. Changing the porosity of the bubble generator, different
bubbles size can be created, thus altering the total surface area of the
bubbles. Specially, if the mode of collection depends on the removed ion
and the surfactant ion meeting on the bubble surface, the residence time of
bubble must be sufficiently high to allow this proceed up to completion, this
sometimes can be over passed by finer bubbles. If it is not, some surfactant
floats wastefully and complete removal of the ion with stoichiometric
amount of surfactant becomes impossible.
Sulaymon and Mohammed (2010) studies the effect of hole diameters
(0.05 and 0.1 cm) of the gas distributer on the bubble diameters on
emulsified oil removal by flotation column.They concluded that the bubble
diameter increase since the increase in hole diameter resulted in a decrease
in bubble rise velocity for a given gas flow rate. New correlations of bubble
diameter were derived:

=0.023[ ]0.053 [ ] 0.08 [ ] 0.12 (2-1)

Where:

liquid viscosity , surface tension , liquid density , g acceleration due to


gravity

2.8 Foam or Froths


Foam is produced when air or other gas is introduced beneath the surface
of a liquid. The liquid expands to enclose the gas within a thin film called a
lamella. In order to create foam; the liquid must contain a surface-
active solute that is adsorbed at the liquid/gas interface. Foam stability and
structure are known to play a significant role in flotation performance.

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Recent studies have shown that changes in concentrate grade and recovery
can be linked to changes in froth stability as operating parameters are varied
(Banford et al., 1998; Ventura-Medina and Cilliers, 2002; Barbian et al.,
2005; Hadler et al., 2009). In these studies, froth stability has been
quantified using air recovery.
A stable foam (or more correctly a persistent foam, since foams are not
thermodynamically stable due to their higher high interfacial free energy) is
produced when the rupture of the lamellae is prevented even after most of
the liquid has drained out of it. The stability of foam can be quantified as the
time that elapses between its formation and its collapse. In general, the
longer the collapsing time, the more stable the foam (Pugh et al., 1996).
One of the simplest methods for determining the stability of foam is by
measuring the height of a foam column as a function of time (Wilson, 1996).
There are three basic mechanisms involved in foam collapse: drainage,
film rupture and bubble coalescence .Several forces act on the thin films in
the foam structures and causes either stabilising or destabilising effects.
Drainage of liquid from the foam lamellae due to gravity is a
destabilising effect, which results in film thinning. At a critical thickness of
50-100 Ao the film will rupture due to attractive Vander Waals Forces
leading to coalescence of two bubbles(Wilson, 1989).
The dependence of foam stability on surfactant depends upon a number
of factors, including the chemical structure of the surfactants, surfactant
concentration, etc. Tamura et al. (1998) suggested in their recent study that
surfactant structure plays a role in the drainage of foam films. For a nonionic
surfactant, increases the hydrocarbon chain length results in an increase
intermolecular hydrophobic interaction in the adsorbed surfactant and thus
an increase in the foam films lifetime. By contrast, increase the relative size

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of the hydrophilic group causes decrease in the hydrophobic interaction,


resulting in less foam stability.
In case of cationic surfactants, the same effect of hydrocarbon chain
length on film stability has also been observed. For example, there is a sharp
increase in film stability of cetyl triethylammonium bromide (CTAB) when
increasing the hydrocarbon chain length from C12to C14 (Bergeron, 1997).
Pugh et al. (1996) suggested that surfactant concentration can plays a role
in foam stability. If the surfactant solution is too dilute, the surface tension
of the solution does not sufficiently differ from that of pure solvent to
counteract the film thinning effect. On the other hand, if the surfactant
concentration is too high, well above its (CMC), the available surfactant will
be such that no gradient is formed.
Velikov et al. (1997), however, have demonstrated that the lifetime of
foam films increases linearly with the logarithm of surfactant concentration,
regardless of type of films or surfactant, and not only below the CMC but
also much above this concentration threshold.
For ion flotation to be economically viable, it would be essential that
both the metal values and the collector can be recovered from the foam.
Sreenivasarao and Doyle (1995) investigated four different methods for
decomposing metaldodecylsulfate complexes generated by ion flotation.
These were precipitation of hydroxides, precipitation of sulfides, chemical
stripping and electrolysis. Electrolysis appears to be more promising than
other approaches for recovering metals and regenerating collector.
Electrolysis has been used to decompose precious metalcollector
complexes (Nicol et al., 1992). Both cadmium and copper were recovered
from dodecylsulfate solutions using a graphite plate anode and a steel wool
cathode. Fig. 2.4 shows a conceptual flow sheet for using ion flotation to
remove residual metal ions from a process effluent, using dodecylsulfate

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complexes in to a separate foam phase. The effluent is first conditioned


with a recycled solution containing collector in the acidic form. Ion flotation
separates metaldodecylsulfate complexes into a separate foam phase,
yielding a detoxified effluent. The foam fraction would then be broken, and
the more concentrated solution would undergo electrolysis, which would
yield metal and a solution of the collector. The latter could be recycled
directly back to conditioning.
Process Effluent

Conditioning
Solution

Foam
Ion flotation

HDS- Rich solution Foam Treated solution discharge


Electrolysis

Metal product

Figure 2.4 flow chart showing how ion flotation with dodecylsulfate and
electrolytic metal recovery could be used to remove residual metal ions from
a process effluent (Doyle et al., 2003)

2.9 Modifiers
This class of reagents covers all chemicals whose principal function is
neither collecting nor frothing. These may be further divided into
depressants, activators and pH regulators. A depressant is any chemical
which inhibits or prevents the adsorption of a collector by a mineral particle
and thereby prevents its flotation. An activator prepares the mineral surface

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to enhance the adsorption of the collector. PH regulators adjust the pulp pH


to give optimum performance for a particular reagent and mineral ore (Gupta
et al., 2006).

2.10 pH of the system


Regulators such as lime, caustic soda, soda ash, and sulfuric acid are used
to control or adjust pH, a very critical factor in many flotation separations
(Perry et al., 1997).The price is not the criteria to follow in deciding which
additive to use, since the side effects of CL-, SO4-2, NO3- ions may play a
very significant role in some systems (Lu et al., 2005).
There are a variety of reasons trying to explain this influence, among
them the main seem to be (Zouboulis et al., 1990):
In any system the ionic competition of the solution will be different at
different initial pH ,i.e. change may occur in the surface charge on the ion
to be removed ,due to hydrolysis or the formation of several complexes
,or the pH value should be such that the surfactant is in desired state of
ionization.
Variation of the pH leads to the change in the nature of the process; the
ion may be precipitated, for instance, as hydroxide, i.e. ion flotation will
become precipitate flotation.
The process may be suppressed by the increased ionic strength, due to
extreme pH changes and by species being favoured in these solutions.
Rubin and Johnson (1967) studies the effect of pH onion and precipitate
flotation systems using sodium laurylsulfate as anionic surfactant to remove
both soluble and insoluble copper (II), they found that the best flotation
results were noticed at pH value of approximately 10 and there was a good
agreement between experimental data curve and the optimum precipitation
area of Cu (OH) 2, obtained from theoretical solubility data.

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Medina et al. (2005) studies the kinetics removal of Cr (III) flotation


using sodium dodecylsulfate and ethanol, they found that pH played an
important role in foam separation techniques and the best flotation results
were obtained in the pH range between 6 and 9 .They suggested that the
formation of Cr(OH)3 precipitation could explain the higher recovery at that
pH and for more alkaline pH the superficial charge of the precipitate
changed from positive to negative led to decreasing the removal ratio using
sodium dodecylsulfate.

2.11 Flotation kinetics


Flotation kinetics studies the variation of floated concentration according
to flotation time. Studies of flotation kinetics are useful in the elucidation of
the mechanism of the process, and serve as predictive tools in the
implementation of flotation technology (Williams and Hanumanth, 1992).
The concentrate obtained from a batch flotation cell changes in character
with time as the particles floating change in size, grade and quantity. The
recovery of any particular mineral rises to an asymptotic value R which is
generally less than 100%.The rate of recovery at time t is given by the slope
of the tangent to the curve at t. There is a direct relationship between the rate
of flotation and the amount of floatable material remaining in the cell that is:
Flotation rate = k x (concentration in the cell) n (2-2)
The flotation rate is equal to the rate of change of concentration of floatable
material in the cell, and Eq. (2-2) may be re-written as the differential:

( ) =k Cn (2-3)

This is the basic rate equation, in which the value of n denotes the order of
the equation and k is the flotation rate constant. Integration of Eq. (2-3) with
n = 1 (first order) gives:

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C = Coe-kt (2-4)
Where Co= the concentration of valuable material at zero time, and C = the
concentration of valuable material remaining at time t. Taking the ln of Eq.
(2-4):
ln ( ) = -kt (2-5)

And if the experimental values of ln (C/Co) are plotted against t, the graph
should be a straight line of slope k if n = 1(Gupta et al., 2006).
The rate constant, k, within this equation conveys how rapidly one species
floats. A high rate constant indicates that certain species floats quickly while
a low rate constant indicates slow flotation.

2.12 Previous Related Research


A number of studies have addressed the removal of metals from waste
waters using foam separation techniques.
Rubin and lapp (1971) studied the effect of pH and ionic strength on the
foam separation of zinc by using different concentrations of sodium lauryl
sulfate as the collector .At low pH, Zn+2 ion was removed by ion flotation,
but above pH 8, zinc (OH) 2 was removed by precipitate flotation,
The addition of salts adversely affected the removal of zinc, Above pH 8,
zinc was present as the insoluble hydroxide and was removed by
precipitate flotation which much less sensitive to ionic strength and collector
concentration .This results indicated that precipitate flotation was a more
efficient removal process than ion flotation of soluble metals species.
Karger and miller (1969) and Karger et al. (1968) investigated the foam
flotation of chlorocomplexes of Fe+3, Hg+2, and Co+2 using a cationic
surfactant; these metals can be separated by controlling the chloride
concentration.

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Skrylev and Dashuk (1975) investigated cadmium and zinc removal by


flotation with potassium caproate; the removal efficiency increased with
small additions of electrolytes (such NaCl, Mgcl2, and CaCl2).
Somasundaran (1975) investigated a number of factors that influence
ion and precipitate flotation, including the molecular chain length of
the surfactant, surfactant/collector concentration, solution pH, ionic strength,
metal-ion concentration, concentration of complexion agent, and physical
variables (such as gas flow rate and temperature), Their results indicated that
an increase in the length of the non polar part of the surfactant generally
causes an increase in the adsorption of surfactant at interfaces, which
enhances mineral separations.
Walkowiak et al. (1976) investigated the selective foam fractionation of
zinc, cadmium, mercury, and gold chloride, nearly 100% removal was
achieved for each metal.
Kim and Zeitlin (1979) used an adsorption-colloid-flotation process
(which used a negatively charged ferric hydroxide collector, a cationic
surfactant, dodecylamine, and air) to remove copper and zinc from sea water
in less than 5 min. The mean recovery of copper and zinc was 95.0% and
94.0%, respectively.
Currin et al. (1979) investigated the compatibility of the adsorbing colloid
flotation of Cu+2 with Fe (OH) 3 and sodium lauryl sulfate (NLS) with
variety of precipitation pretreatment techniques. They found Cu+2 levels,
already quite low after precipitation with lime, were readily reduced to even
lower levels by foam flotation with Fe(OH)3and NLS.
Preliminary batch studies conducted by Thackston et al. (1980) showed
that the optimum pH for the removal of lead was approximately 6.5 and that
increasing ionic strength was detrimental to the process. Ferric hydroxide
was much more effective for adsorbing lead than was aluminum hydroxide

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and sodium hydroxide was a more effective neutralizing agent than was
sodium carbonate (soda ash).
Matis et al., 1991 examined the removal of two metal ions copper and
chromates by applying two flotation techniques: precipitate and adsorbing
colloid flotation. They deduced the conclusions that; collector (SDS) and
frother (ethanol) concentrations had no significant effect on copper removal,
collector concentration had no effect for chromium removal and comparison
of the three flotation techniques (precipitate, sorptive and adsorbing colloid
flotation),in a hybrid configuration ,revealed that precipitate flotation had the
better influence on membrane performance.
Zouboulis et al.,1995 investigated the recovery of silver from dilute
aqueous solutions containing complexion agent by ion flotation .In this
study ,the objective was to establish the optimum conditions such as pH,
surfactant ,silver and thiosulphate concentrations in order to apply the
method to synthetic solutions. Experiments were performed using cationic
surfactant dodecyl amine (DA), as frother ethanol .High recoveries of silver
from aqueous solutions containing thiosulphates and optimum conditions for
the recovery of silver were obtained.
Experimental investigations on the removal of Cd (II) from aqueous
solution were carried out using a foam separation technique with sodium
lauryl sulfate and sodium laurate by Choi et al., 1998.The effects of pH,
surfactant, and foreign ions on the efficiency of Cd (II) removal rate
discussed. Foam flotation with sodium laurate gave better removal
efficiency than with sodium lauryl sulfate
Charewicz et al., 1999 examined the batch flotation of zinc (II) and silver
(I) ions from dilute aqueous solutions with sodium dodecyl sulphate and
ammonium tetradecylsulfonate as anionic surfactants and with cetylpy-
ridinium chloride as a cationic surfactant. Also, they studied the effect

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of inorganic ligands (thiosulphates, thiocyanates) on the selectivity of ion
flotation of Zn (II) and Ag (I) ions. They found that Zn (II) and Ag (I) could
be separated from diluted aqueous solutions with anionic surfactants since
Zn+2 cations exhibited a much higher affinity for a surfactant than did Ag+
cations. The separation of metal ions was also possible when solution
contains thiosulphate or thiocyanate ligands.
The removal of Cd (II) using SDS as a collector was studied by Scorzelli
etal.,1999.They also studied in the effect of frothers and the surface tension
of the initial solutions. Iso-propanol and methylisobutylcarbinol (MIBC)
were used as frothers. Characterization of the sublate by scanning electron
microscopy (SEM) were also examined to understand what occurs during
ion flotation. Surface tension data and SEM results showed the reduction in
floatability which was related to the adsorption of SDS at interface liquid-
gas. The best recovery was obtained as 88.2% in the presence of SDS.
A thermodynamic approach was investigated to model the removal of
cupric ion from (sodium dodecylsulphate)SDS-Cu,(sodium tetradecyl
sulphate)STS-Cu and (sodium hexadecylsulphate)SHS-Cu ion flotation
systems by liu et al.,2001.They obtained surface tension data a wide
concentration range of each alkylsulphate-copper solution. They used the
data to fit analytical regression equation and differentiated to generate an
expression for the metal ion adsorption densities. They demonstrated that the
more active collectors gave faster metal removal kinetics and were capable
of attaining much lower steady-state copper concentrations and they built up
a model for the copper removal kinetics.
Doyle et al., 2003 observed the fundamental characteristics for ion
flotation in the context for their implications for commercial applications.
These characteristics included the kinetics for metal ion removal, the ability
to recover metal values from the foam product, the ability to separate ions

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selectively from mixed solutions and a comparison of the performance of ion
flotation with other separation methods.
Doyle et al., 2003 reported that the effect of a neutral chelating ligands,
triethylenetetraamine (Trien) on the ability to separate copper (II) and
calcium (II) ions and compared the ion flotation behavior of Cu+2 and Ni+2
ions with the behavior of Cu-Trien and Ni-Trien complexes .In experiments,
SDS was used as the collector .They concluded that copper was removed
preferentially, whereas in the absence of Trien, the calcium was removed.
Trien was shown markedly increase the removal rates of Cu+2, Ni+2 during
ion flotation with SDS and lower the steady state concentration reached.
Surface tension measurements confirmed that Trien enhanced the surface
activity and adsorption density for SDS Cu (II) and SDS-Ni (II) solutions.
A study concerning the kinetics of Cu+2 ion separating by precipitate
flotation using alkyl amine type (laurylamine) and alkylammonium salt
(lauryltrimethylammonium chloride)as cationic collectors and alkylsulphate
and alkylcarboxilic type (sodium laurylsulphate and sodium oleate) as
anionic collectors was presented by Stoica et al. ,2003.Obtained data were
used to verify the classical the first order model and there other first order
models, adjusted to the classical model.They found Cu(II)hydroxide species
separation using precipitate flotation followed an overall first order kinetic.
Zouboulis et al., 2003 investigated the removal of Zinc and chromium
ions from aqueous solutions by application of a two-stage separation
process. The first part consisted of the metal ions sorption onto an
appropriate sorbent material and successive flotation followed as the second
part. The biologically produced surface active agents Surfactin-105
and Lichenysin-A were as alternative collectors for flotation methods. The
conclusion was drawn from experimental data; biosurfactants effectively
removed sorbent material and presented. Both biosurfactants removed
Chapter Two
Literature Survey

chromium ions after sorption studies. Surfactin was proved to be an effective


surfactant for the removal of zinc ions after sorption process.
Lazaridis et al., 2004 was investigated the recovery of copper ions from
wastewater. They used three different mechanisms: ion flotation using
xanthates, precipitate flotation generating copper hydroxide and sorptive
flotation using zeolites as a sorbent material. Ion and sorptive flotation
methods were found to be effective for copper removal while the
precipitation method failed.
The removal of chromium (III) by precipitate flotation from dilute
aqueous solutions, using sodium dodecylsulfate as anionic collector and
ethanol as a frother was investigated by Medina et al.,2005.The adequate
experimental conditions were obtained through precipitate flotation such as
SDS and ethanol concentration and gas flow rate. They studied the results
led to a first order model for the removal of chromium (III) by precipitate
flotation.
Ghazy et al., 2008 developed a simple, rapid and economic procedure
for copper (II) and lead (II) removal under the optimum conditions. It
was based on the complex formation between Cu+2 and Pb+2 ions and
diphenylcarbazone (HDPC) followed by flotation with oleic acid (HOL)
surfactant. The different parameters (namely: solution pH, HDPC, HOL,
copper and lead concentrations, ionic strength, temperature and the presence
of foreign ions) influencing the flotation process were examined. Nearly,
100% of Cu+2 and Pb+2 ions were removed from aqueous solutions at pH 6
and 7, respectively at room temperature (25Co).
Liu et al.,2009 Investigated the Ion Flotation of Co+2, Ni+2, and Cu+2
Using Dodecyldiethylenetriamine (Ddien),They obtained that a chelating
surfactant, dodecyldiethylenetriamine (Ddien), could selectively remove one
metal ion over others at different pH values. Selectivity was attributed to the
Chapter Two
Literature Survey

formation of surface-active chelated species at specific pH.


A system for removal of Cu+2 from aqueous solution by foam
fractionation using Dodecyl Benzenesulfonic acid (the anionic surfactant
used in this study) was proposed by Zhang et al., 2009. The effects of pH,
gas flow rate, surfactant concentration and froth/solution ratio on the
removal rate and the enrichment ratio were studied to optimize
the conditions. They concluded that the removal rate increased with gas
flow rate decreased, surfactant concentration increased and the froth/solution
ratio increased, and was higher at pH4.05.0 than at other pH value. Under
the optimum conditions, the removal rate was 97.2% and the enrichment
was 53.0.
Abryutin et al., 2010 investigated the regularities of the ion flotation
of copper by using sodium diethyldithiocarbamate (DEDTK) as the
collector. The results of investigation into the structure of the obtained
precipitates of copper DEDTK were presented. The distributions over the
size of air bubbles were analyzed and the effect that a series of factors had
on the degree of removal of copper ions from model solutions was
investigated also.
The aim of the present work is study the copper flotation in a column
flotation and to study the effects of various variables at room temperature
on the separation efficiency such as gas flow rate ,hole diameter of gas
distributer, initial copper concentration ,surfactant types and concentration
,pH range, ethanol concentration and ionic strength .
Chapter Three
EXPERIMENTAL WORK AND
PROCEDURE
3.1 Materials
3.1.1 Reagents
Two types of surfactants, Sodium dodecyl sulfate (SDS, 99%) and
Hexadecyltrimethyl ammonium bromides (HTAB, 99%) from Fisher
Scientific were used as anionic and cationic collectors, respectively. The
first type is a white powder material with a chemical structure of
(C12H25OSO3Na).The second type is a white powder material with a
chemical structure of (C12H42BrN). A summary of these surfactants with
some common characteristics are given in Table 3.1.Ethanol (C2H5OH) from
Lancaster Synthesis was used as frother. Copper chloride dehydrates
(CuCL2.2H2O, purity=99.5%wt, M.wt=170.482g/mole) and sodium chloride
(NaCl, purity=99.5%wt) from Fisher Scientific were used as the colligend
and the ionic strength adjuster, respectively. Sulfuric acid (H2SO4) and
caustic soda (NaOH) were used for pH adjustments.
Table 3.1.Selected Properties of Surfactants Used in This Study

Commercial Name Hydrophobic Hydrophilic Molecular C.M.CX10-3


Group Group Weight Moles/L
(g/mol)
Anionic Surfactant
Na-Dodecyl Sulfate Dodecyl Sulfate 288.38 8.25
Cationic Surfactant
Hexadecyltrimethyl Hexadecyl Ammonium 364.45 92.0
ammonium
bromide

Chapter Three
Experimental Work and Procedure

3.1.2 Gas
Air was the type of gas used in the present study (compressed at 1 bar up
to 7 bars) was supplied by a compressor.

3.2 General Description and Procedure

3.2.1 General Description


The foam flotation tests were carried out in a bubble column (acrylic) of
6 cm inside diameter and 120 cm in height. Figure 3.1 and Figure 3.2 show a
schematic and photographic diagram of experimental apparatus. Air supplied
by the compressor was fed to the column through a pre-calibrated rotameter.
Air entered the column was dispersed as bubbles in to liquid. Feed inter with
different metal concentration (25 up to 200 ppm) was poured gently at the
top of the column. At the same time, the column was pressurized so as not to
weep the liquid through the holes. Two perforated plates of the air
distributor were used. The first one has 20 holes with 0.1 cm diameter, and
the second one has 25 holes with 0.05 cm diameter. The holes are arranges
in the equilatered triangular pitch through the whole area which are located
inside the column. The column was operated at batch mode as far as the
liquid phase and continuous flow with respect to air. This column contains
six taps of 0.2 cm inside diameter, these taps arranged at interval of 15cm
and used to draw samples from the column.

3.2.2 Preparation of Solution


Synthetic polluted water samples containing maximum concentration of
copper (200mg/l) were prepared by dissolving (CuCl2.2H2O) in distilled
water. Surfactants and ethanol were added to the synthetic polluted
water. Solution pH was adjusted to a desired value using H2SO4 or NaOH.

Chapter Three
Experimental Work and Procedure

The required mass of CuCl2.2H2O was calculated as follows:


.
=
.
Where:
W: Weight of CuCl2.2H2O (g)
V: Volume of solution(l)
Ci: Initial concentration of copper ions in solution (0.2 g/l)
M.wt: Molecular weight of CuCl2.2H2O (170.482 g/mol)
At.wt: Atomic weight of copper (63.546 g/mole)

Then the solution was placed in the flotation column. Foam samples were
taken at preset time intervals as 5, 10, 15, 20, 25, 30, 35 and 40 minutes. A
port 0.45 m above the base was used for periodic sampling. About 3ml of
solution was drained from the port before withdrawing each sample; samples
were withdrawn slowly, to minimize entrainment of air bubbles. Between
experiments, the column was cleaned using HNO3, and then rinsed three
times with double distilled water. The apparatus used in the experiment
were:
pH-meter (WTW,Sr.Nr:08490207)
Atomic Absorption Spectrometry (AAS) (Perkin Elmer, Sr.Nr:1159A)
Chapter Three
Experimental Work and Procedure

6 cm

30cm
Foam
15cm Flotation Column

15cm
15cm
15cm Rotameter Pressure Gauges

15cm
15cm Filter Air

Distributor

Needle Valve

Figure 3.1Schematic diagram of the experimental set-up.


Figure 3.2 Experimental set-up of the flotation column used in the present
study .

Chapter Four
RESULTS AND DISCUSSION

4.1 Effect of pH
Several works related to the foam separation techniques point out that pH
plays an important role in flotation. Depending on pH, different interfacial
properties and reaction routes may be found (Matis and Mavros, 1991).
The effect of pH on the recovery of copper by bubble column is shown in
Fig.4.1by plotting the removal ratios versus time at various pH values .As
shown in this figure the removal ratios decreases suddenly after
approximately ten minute from the beginning of the run ,then ,these ratios
began to decrease slowly with time. It was found that the highest removal
achieved when the pH of the solution was 10.
This result was similar to Polat and Erdogan (2007).They suggested that
the charge of copper ion was positive Cu+2, CuOH+ at pH below 10 whereas
they are negatively charged Cu(OH)-3 and Cu(OH)4-2 at pH values greater
than 10. At and around pH 10, precipitation of neutral Cu(OH)2 takes place.
The formation of the precipitation of Cu(OH)2 can explain the higher
recovery for pH values at and around 10.
The removal rate constant at various pH was found by plotting ln (Co/C)
against time according to equation (2.5).The rate constant obtained at
various pH values were plotted in fig.4.2 and their values were tabulated in
Table 4.1.It can be seen that the higher rate constant (k=8.7 10-2) is
obtained at pH=10 .

Chapter Four
Results and Discussion

pH=4,SDS
1 pH=6,SDS
0.9 pH=8,SDS
0.8 pH=10,SDS
0.7 pH=12,SDS

0.6
C/Co

0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.1 Effect of pH on the removal ratio of copper ions (Co=100mg/l;


SDS=75 mg/l; Q =250 ml/min; ethanol=1%,do=1mm).
0.1
0.09
0.08
0.07

Rate constant (1/min)


0.06
0.05
0.04
0.03
0.02
0.01
0
0 1 2 3 4 5 6 7 8 9 10 11 12
pH

Figure 4.2 Rate constant at various pH (Co=100mg/l; Q=250ml/min;


SDS=75 mg/l; ethanol=1%.do=1mm).

Chapter Four
Results and Discussion

Table 4.1 Rate constants at various pH

pH k102 (min-1)

4 0.6
6 1.2
8 4.0
10 8.7
12 2.4

4.2 Effect of surfactant type


The type of surfactant plays a significant role in foam flotation. The type
of collector needed depends on the pH of the solution. In general, anionic
collectors are needed at low pH because the metal ions are in cationic forms.
At very high pH, cationic collectors would be needed if the metal ions were
present as anions (Zoubolis et al., 1987).
The removal rate of copper from water was studied at two different types
of surfactant (sodium dodecyl sulfate and Hexadecyltrimethyl ammonium
bromide) in order to show the effect of adding anionic and cationic
surfactant on the removal rate of copper ions. The effect are shown in
Fig.4.3 by plotting the (C/C0) ratio versus time at the two surfactant types.
From this figure, the anionic surfactant (SDS) is more efficient than the
cationic surfactant (HTAB) and at pH lower than 10 no significant removal
rate was obtained using (HTAB) and the removal rate increases for pH more
than 10.

Chapter Four
Results and Discussion

1 pH=4,SDS
pH=6,SDS
0.9
pH=8,SDS
0.8
pH=10,SDS
0.7
pH=12,SDS
0.6 pH=10,HTAB
C/Co

0.5 pH=12, HTAB


0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
Figure 4.3 Effect of surfactant type on the removal ratio of copper (Co=100
mg/l;Q=250ml/min;SDS=75mg/l; HTAB=75mg/l; ethanol = 1 % ,do =1 mm).

4.3 Effect of surfactant concentration


The key to floatability (or non floatability) of chemical species is
hydrophobicity. Substances are rendered hydrophobic by addition of the
appropriate collector, in which the polar groups are eliminated by adsorption
leaving non-polar groups exposed to solution. An important factor relates to
the ratio of collector to metal ion. Usually a small excess of collector is
added to guarantee maximum removal of the metallic ions in solution.
Excessive collector should be avoided, not only due to higher cost, but also
because of other negative effects, such as large foam losses, micelle
formation, competition between the metal-collector complex and free
collector ions for bubble surface sites and the potential toxicity of residuals
amounts of collector in the effluent (Scorzelli et al., 1999).The effect of
different sodium dodecylsulfate (SDS) concentration in the copper removal

Chapter Four
Results and Discussion

at pH=10 and pH=4 is shown in Fig.4.7 and Fig.4.8 respectively. It can be


seen that collector concentrations has much greater effect at pH =4 than the
effect at pH=10. According to (Lemlich, 1972), the copper ions are
completely soluble at low pH and the removal rates are strongly dependent
on collector concentration requiring higher collector concentration for
complete removal and at high pH the copper ions are insoluble and the
removal rates are considerably less affected at collector ratios of 0.2 or
greater.
Fig.4.7 shows the effect of increasing SDS concentration at pH=10 where
the precipitate takes place. It can be seen that there is no significant
difference in removal rates with increasing SDS concentration from 25 mg/l
to75 mg/l. Further increasing in surfactant concentration results in
decreasing in the copper removal .The decreasing in the copper removal for
raised collector concentration can be due to competition between coligend-
collector complex and free ion collectors for a place in the surface of the
bubble (Medina et al., 2005).
The effect of different SDS concentrations on the copper removal rate at
pH=4 is presented in Fig.4.8. From this figure, it can be seen that at low
surfactant concentration (75 mg/l) low copper removal (38%) was obtained.
This may be attributed to the presence of insufficient amounts of surfactant
required for complete flotation (Ghazy et al., 2008).The separation
efficiency improves to about (68.2%) with increasing surfactant
concentrations up to (350 mg/l).
The removal rate constant at various SDS concentrations were found by
plotting ln (C/Co) against the time. The slope of these lines gives the rate
constants in Fig.4.9 and their values were tabulated in Table 4.3. The
experimental results seem to be a little bit deviated from the first order

Chapter Four
Results and Discussion

kinetic model proposed by Gupta et al. (2006), although the deviation is not
too significant.
1 SDS=125 mg/l
0.9 SDS=75 mg/l
0.8 SDS=25 mg/l
0.7
0.6
0.5
C/Co

0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time (min)

Figure 4.4 Effect of surfactant concentration on the removal rate of copper


(pH=10; Co=100 mg/l; Q=250 ml/min; ethanol=1%;do=1mm).

1
SDS=75mg/l
0.9
0.8 SDS=225mg/l

0.7 SDS=350mg/l
0.6
0.5
C/Co

0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.5 Effect of surfactant concentration on the removal rate of copper


(pH=4; Co=25 mg/l; Q=250 ml/min; ethanol=1%,do=1mm).

Chapter Four
Results and Discussion
0

-0.5
125 mg/l
-1
75 mg/l
-1.5
25 mg/l
-2
ln(C/Co)
-2.5

-3

-3.5

-4

-4.5

-5
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.6 ln (C/Co) versus time at different SDS concentration. (pH=10;


Co=100 mg/l; Q=250 ml/min; ethanol=1%,do=1mm).

Table 4.2 Rate constant at various SDS concentrations

Co(mg/l) k102(min-1) n

25 7.6 1.080

75 8.7 1.065

125 6.3 0.901

Chapter Four
Results and Discussion
4.4 Effect of initial copper concentration
The removal rate of copper at various initial copper concentration is
shown in Fig.4.4 and Fig.4.5 by plotting (C/C0) rate versus time at pH=10
and pH=4 respectively. From these figures, it was found that copper
concentration has a much greater effect on removal rate at pH=4 than at
pH=10.
Fig.4.4 shows the effect of increasing copper concentration at pH=10
where the precipitate take place. It can be seen that there is no significant
difference in removal rate with increasing copper concentration from
100mg/l to 200mg/l. However at low copper concentration (25mg/l) the
removal rate decreased because of large surfactant: copper ion ratio which
cause competition, for bubble surface, between the metalcollector product
and free collector ions (Shakir et al., 2010).
Fig.4.5 shows the effect of increasing copper concentration at pH=4.
It can be seen that decreasing copper concentration leads to increase
removal rate. This result was similar to Zouboulis et al. (1990).They
suggested that an increased metal ion concentration increased collector
required for same percent removal.
The removal of copper ions at pH=10 where copper hydroxide
precipitation take place was more efficient, rapid and virtually complete
within a relatively short time than the removal of copper ions at pH=4.It was
much less sensitive to the difference in copper concentration than removal at
pH=4 and it becomes clear that in each system to be separated, certain
optimum ratio of reagents exists.
The removal rate constants at various copper concentrations were
found and their values were tabulated in Table 4.2.

Chapter Four
Results and Discussion
1
0.9 cu=25 mg/l

0.8 cu=100 mg/l


0.7 cu=200 mg/l
0.6
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40

Figure 4.7 Effect of copper concentration on the removal rate (pH=10; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm).

1
0.9
0.8
0.7
0.6
C/C0

0.5
0.4
Cu=25mg/l
0.3
Cu=50mg/l
0.2
Cu=100mg/l
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.8 Effect of copper concentration on the removal rate (pH=4; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm).
Chapter Four
Results and Discussion

Table 4.3 Rate constant at various initial copper concentrations

Co(mg/l) k102(min-1)

25 4.7

100 8.7

200 7.0

4.5 Effect of air flow rates


When gas is blown into a liquid through a hole of the distributor, the size
of bubbles varies with the gas flow rate, the diameter of the holes, the
physical properties of the liquid and the volume of the gas chamber
(Mohammed, 2004).
The effect of gas flow rate (100,250 and 500ml/min) on the removal
efficiency of copper in the bubble column was investigated .The results are
shown in Fig.4.10 and Fig.4.11 for pH=4 and pH=10 respectively. The data
presented in these figures indicate that the removal rate was highly affected
by the gas flow rate. As gas flow rate increased, the removal ratio increased,
This is because increased gas flow rate causes early bubble detachment,
large fluid activities (stress)at the bottom section and bubble coalescence
and (mostly) break up (Sulaymon and Mohammed, 2010).This results in a
large number of small bubbles which leads to increasing surface area
available for adsorption metal-collector. However, higher gas flow rate
results in decreasing the removal rate from the maximum due to the
redispersion of some of the metal collectorprecipitate product back in to the
bulk solution.
Chapter Four
Results and Discussion

1
0.9 Q=100 ml/min

0.8 Q=250 ml/min


0.7 Q=500 ml/min
0.6
0.5
C/Co

0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.9 Effect of gas flow rate on the removal rate of copper (pH=4;
Co=25 mg/l; SDS=350 mg/l; ethanol=1%,do=1mm).

1
0.9
0.8 Q=100 ml/min
0.7
Q=250 ml/min
0.6
Q=500 ml/min
0.5
C/Co

0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.10 Effect of gas flow rate on the removal rate of copper (pH=10;
Co=100 mg / l; SDS=75 mg/l; ethanol=1%,do=1mm).
Chapter Four
Results and Discussion

The removal rate constants at various gas flow rate were tabulated in
Table 4.4.It can be seen that the rate constant increased with increasing gas
flow rate.

Table 4.4 Rate constants at various gas flow rate.

Q(ml/min) k102(min-1)

100 3.0

250 8.7

500 4.6

The effect of different hole diameter of the gas distributor on the


removal rate was shown in Fig.4.12.It can be noticed that the removal rate
decreases with increasing hole diameter. This decreasing in the removal rate
is due that to increased bubble diameter as a results of increased the hole
diameter of air distributor since the increase in hole diameter resulted in a
decrease in bubble rise velocity for a given flow rate (Sulaymon and
Mohammed, 2010). Decreasing bubble diameter leads to increase the surface
area for metal-collector adsorption and increasing probability of collision
for smaller bubbles.
Chapter Four
Results and Discussion

1
0.9
d=1mm
0.8
d=o.5 mm
0.7
0.6
0.5
C/Co

0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time (min)

Figure 4.11 Effect of hole diameter of the gas distributor on the removal rate
of copper(pH=4;Co=25mg/l;SDS=350mg/l; Q=250ml/min; ethanol = 1 % ).

4.6 Effect of frothers


The effect of adding ethanol to the copper ions removal is shown in Fig.
4.13 and Fig.4.14 for pH=4 and pH=10 respectively. These figures show that
adding ethanol leads to increase removal rate of copper ions and at higher
ethanol concentration the efficiency decreased. Increasing the removal
efficiency with increasing in ethanol concentration in the solution is
presumably attributed to decrease of degree of coalescence of gas bubbles
leading to formation of more fine bubbles (Cho and Laskowski, 2002).
Consequently, the surface area of the gas phase increases leading to
improvement in flotation efficiency. However, an increase in ethanol
concentration over a certain value results in reduction in the removal
efficiency. This reduction in removal is attributed to that on elevation of
frother concentration over a particular concentration (the critical coalescence
concentration) the bubble size becomes no longer controlled by coalescence

Chapter Four
Results and Discussion

but will strongly depend on the sparger geometry and hydrodynamic


conditions (Shakir et al.,2010). Also at the higher ethanol concentrations,
the number of sites on the interface liquid-gas available for metal- collector
complex adsorption will be reduced due to adsorption of alcohol molecules,
which may lower metal removal (Medina et al., 2005).

without ethanol
1
0.9 ethanol=1%

0.8 ethanol=2%
0.7
0.6
C/Co

0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.12 Effect of ethanol concentration on the removal rate of copper


(pH=4; Co=25 mg/l; SDS=350 mg/l; Q=250 ml/min, do=1mm).
Chapter Four
Results and Discussion

1
without ethanol
0.9
ethanol=1%
0.8
0.7 ethanol=2%

0.6
C/Co

0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.13 Effect of ethanol concentration on the removal rate of copper


(pH=10; Co =100 mg/l; SDS=75 mg/l; Q =250 ml/min, do=1mm).

The removal rate constant at various ethanol concentration were tabulated


in Table 4.5.It can be seen that the rate constant increased with added
ethanol while further increased in ethanol decreased the rate constant.

Table 4.5 Rate constants at various ethanol concentrations

Ethanol concentration k102(min-1)


(%)

Without ethanol 4.2

1 8.7
2 5.2

Chapter Four
Results and Discussion

4.7 Effect of ionic strength


The effect of adding NaCl to the copper ions removal at pH=4 and
pH=10 was shown in Fig.4.15 and Fig.4.16 respectively .It can be seen that
the removal rate decreases with increasing NaCl concentration. The
explanation of this improvement is that Na ions compete with copper ions so
the metal ions cannot find enough dodecyl sulfate molecules to attach to
(Choi et al., 1998).
The removal rate constants at various NaCl concentrations were found
and tabulated in Table 4.6.It can be seen that the rate constant decreased
with increasing NaCl.

1
0.9 without NaCL

0.8 NaCL=25mg/l
0.7 NaCL=50mg/l
0.6
C/C0

0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40

Time(min)
Figure 4.14 Effect of NaCl concentration on the removal rate of copper
(pH=4; Co=25 mg/l; SDS=350 mg/l; Q=500 ml/min; ethanol = 1% ,
do=1mm).

Chapter Four
Results and Discussion

1
without NaCL
0.9
NaCL=25 mg/l
0.8
NaCL=50 mg/l
0.7
0.6
C/Co

0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)

Figure 4.15 Effect of NaCl concentration on the removal rate of copper


(pH=10; Co =100 mg/l; SDS=75 mg/l; Q =250 ml/min; ethanol = 1 % ,
do=1mm).

Table 4.5 Rate constants at various NaCl concentrations.


NaCl concentration (mg/l) k102 (min-1)
Zero 8.7
25 2.9

50 4.0

Chapter Five
CONCLUSIONS AND
RECOMMENDATIONS
5.1 Conclusions
1. Higher percentage of copper ions removal were achieved at low time (40
min) about 98% for pH=10,Co=100 mg/l, SDS=75 mg/ l , ethanol =
1%,Q=250 ml/min, do=1mm, and about 80% for pH=4,Co=25 mg/l,
SDS=350 mg/l, Q=500 ml/min, ethanol=1%,do=0.5mm.
2. The anionic surfactant (SDS) was found to be more efficient than
cationic surfactant. At pH lower than 10, no significant removal rate was
obtained using HTAB. Maximum removal rate 98% was achieved at pH
= 10 using SDS while maximum removal rate 76% was obtained using
HTAB at pH=12.
3. The best removal of copper ions was achieved at pH= 10.0 and the effect
of various variables at this pH was studied.
a. Increasing the initial copper concentration from 100 to 200 mg/l no
change in the removal rate which was 98% after 40 min of flotation
time; however, decreasing the copper concentration to 25 mg/l
decreased copper removal to 94% due to high surfactant to metal
ratio.
b. Collector concentration had very little affected on the removal rate in
the range 25 to 75 mg/l; however, further increasing of SDS
concentration to 125 mg/l decreased the removal rate to 96%.
c. Added ethanol of 1% increased the removal rate from 91% to 98%;

Chapter Five
Conclusions and Recommendations

however further increased on ethanol to 2% decreased the copper


removal rate to 94.5%.
d. Increasing air flow rate from 100 to 250 ml/min increased the copper
removal rate from 82% to 98%; however, further increasing in air
flow rate to 500 ml/min decreased copper removal to 91.5%.
e. The addition of salt (NaCl) adversely affected the copper removal
rate. Removal rate was found to be 98 % in absence of NaCl and it
decreased from 88% to 81% with increasing salt concentration from
25 to 50 mg/l respectively.
4. The removal of copper ions was also studied at pH=4, which chosen to
represent acidic processing effluents.
a. Lower removal rate about 24 % was obtained for initial copper
concentration of 100 mg/l; however, the copper removal rate
increased from 31% to 38% with decreasing copper concentration to
50 and 25 mg/l respectively.
b. Increasing the SDS concentration from 75to 350 mg/l increased the
copper removal rate up to 68% at copper concentration of 25 mg/l.
c. Increasing air flow rate from (100 to 500 ml/min) increased the
removal rate from (55% to 80%) respectively.
d. Added ethanol of 1% increased the removal rate from 59 to 68%;
however further increased on ethanol to 2% decreased the copper
removal rate to 53%.
e. The addition of salt (NaCl) adversely affected the copper removal
rate. Removal rate was found to be 80% in absence of NaCl and it
decreased to 58.5% to 45% with increasing salt concentration from 25
to 50 mg/l respectively.
f. The effect of the hole size of the gas distributor on the removal rate
of copper ions was studied and it was found that decreasing hole size

Chapter Five Conclusions and Recommendations

from 1mm to 0.5 mm increased the removal rate of copper from


68% to 75%.
5. The rate of flotation was found to be second order and the removal of
copper ions at pH=10 was a more efficient removal process and much
less sensitive to ionic strength and other variables than the removal rate
of copper ions at pH=4, Furthermore, the differences in removals after
only a very few minutes of flotation are very small.

5.2 Recommendation for Further Work


1. Studying the effect of different column diameter on the removal rate.
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compound rather than a single metal and are acidic in nature. So,
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3. Foam flotation should be conducted using actual industrial effluents to
see if there is difference in metal removal or the foam formation between
the synthetic solution and the actual industrial effluents.
4. Finally, the pilot scale study of foam flotation should be under taken and
then the effect of scale up on various physical and chemical parameters
should be examined.
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APPENDIX
Table 5 Residual Copper Concentration at Different pH, Co = 100 mg/l;
SDS=75mg/l, HTAB=75mg/l, Q=250ml/min, Ethanol=1, do=1mm.
Appendix

Table 6 Effect of Initial Copper Concentration on the Removal Rate, pH=10,


Q=250 ml/min, SDS=75 mg/l, Ethanol=1%, do=1mm.

C/Co
Time (min) SDS HTAB

pH=4 pH=6 pH=8 pH=10 pH=12 pH=10 pH=12

5 0.940 0.737 0.697 0.152 0.630 0.791 0.480

10 0.858 0.685 0.549 0.104 0.465 0.775 0.359

15 0.816 0.610 0.446 0.069 0.435 0.746 0.343

20 0.805 0.585 0.332 0.037 0.422 0.723 0.297

25 0.796 0.575 0.300 0.031 0.391 0.642 0.283

30 0.787 0.544 0.262 0.025 0.335 0.597 0.269

35 0.775 0.537 0.212 0.017 0.325 0.548 0.237

40 0.761 0.547 0.191 0.017 0.320 0.518 0.237


C/Co
Time(min) 25 mg/l 100 mg/l 200 mg/l
5 0.120 0.152 0.114
10 0.098 0.104 0.071
15 0.079 0.069 0.054
20 0.067 0.037 0.043
25 0.065 0.031 0.040
30 0.061 0.025 0.035
35 0.061 0.017 0.025
40 0.061 0.017 0.023

Table 7 Effect of Initial Copper Concentration on the Removal Rate, pH=4,


Q=250 ml/min, SDS=75 mg/l, Ethanol=1%, do=1mm.

C/Co
Time(min) 25 mg/l 50 mg/l 100 mg/l
5 0.820 0.868 0.940
10 0.770 0.827 0.858
15 0.699 0.776 0.816
20 0.664 0.739 0.805
25 0.641 0.715 0.796
30 0.624 0.707 0.787
35 0.619 0.694 0.775
40 0.617 0.694 0.761

Appendix

Table 8 C/Co at Various Concentration of SDS, pH=10, Q=250 ml/min, Co


=100 mg/l, Ethanol=1%, do=1mm.

C/Co
Time (min) 25 mg/l 75 mg/l 125 mg/l
5 0.104 0.152 0.212
10 0.122 0.104 0.177
15 0.108 0.069 0.087
20 0.044 0.037 0.083
25 0.039 0.031 0.080
30 0.033 0.025 0.075
35 0.025 0.017 0.049
40 0.025 0.017 0.039

Table 9 C/Co at Various Concentration of SDS, pH=4, Q=250 ml/min, Co


=25 mg/l, Ethanol=1%, do=1mm.

C/Co
Time (min) 75 mg/l 225 mg/l 350 mg/l
5 0.820 0.772 0.725
10 0.770 0.690 0.628
15 0.699 0.613 0.520
20 0.664 0.557 0.467
25 0.641 0.499 0.383
30 0.624 0.458 0.329
35 0.619 0.436 0.320
40 0.617 0.430 0.317

Appendix

Table 10 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=10,
Co =100 mg/l, SDS=75 mg/l, Ethanol=1%, do=1mm.

C/Co
Time (min) 100 ml/min 250 ml/min 500 ml/min
5 0.300 0.152 0.245
10 0.270 0.104 0.150
15 0.240 0.069 0.104
20 0.220 0.037 0.100
25 0.210 0.031 0.097
30 0.185 0.025 0.092
35 0.183 0.017 0.085
40 0.182 0.017 0.085

Table 11 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=4, Co
=25 mg/l, SDS=350 mg/l, Ethanol=1%, do=1mm.

C/Co
Time (min) 100 ml/min 250 ml/min 500 ml/min
5 0.862 0.725 0.655
10 0.748 0.628 0.503
15 0.635 0.520 0.433
20 0.588 0.467 0.378
25 0.525 0.383 0.301
30 0.477 0.329 0.251
35 0.449 0.320 0.210
40 0.448 0.317 0.199

Appendix

Table 12 C/Co at Various Ethanol Concentration, pH=10, Co=100 mg/l, SDS


=75 mg/l, Q =250 ml/min, do=1mm.

C/Co
Time (min) (Zero) (1%) (2%)
5 0.199 0.152 0.155
10 0.119 0.104 0.080
15 0.110 0.069 0.072
20 0.099 0.037 0.068
25 0.093 0.031 0.057
30 0.091 0.025 0.056
35 0.090 0.017 0.055
40 0.090 0.017 0.055

Table 13 C/Co at Various Ethanol Concentration, pH=4, Co=25 mg/l, SDS


=350 mg/l, Q=250 ml/min, do=1mm.

C/Co
Time (min) (Zero) (1%) (2%)
5 0.790 0.725 0.827
10 0.688 0.628 0.716
15 0.590 0.520 0.653
20 0.497 0.467 0.579
25 0.452 0.383 0.527
30 0.422 0.329 0.500
35 0.406 0.320 0.475
40 0.405 0.317 0.470

Appendix

Table14 Effect of NaCl Concentration on the Removal Rate of Copper, pH


=10, Co=100 mg/l, SDS=75 mg/l, Q =250 ml/min. Ethanol=1%, do=1mm.

C/Co
Time (min) Zero 25 mg/l 50 mg/l
5 0.152 0.270 0.350
10 0.104 0.200 0.250
15 0.069 0.155 0.210
20 0.037 0.130 0.200
25 0.031 0.125 0.195
30 0.025 0.124 0.198
35 0.017 0.122 0.194
40 0.017 0.121 0.191

Table15 Effect of NaCl Concentration on the Removal Rate of Copper,


pH=4, Co=25 mg/l, SDS=350 mg/l, Q=500 ml/min, Ethanol=1%, do=1mm.

C/Co
Time (min) Zero 25 mg/l 50 mg/l
5 0.655 0.750 0.844
10 0.503 0.610 0.690
15 0.433 0.510 0.597
20 0.378 0.498 0.576
25 0.301 0.476 0.568
30 0.251 0.450 0.555
35 0.210 0.420 0.552
40 0.199 0.415 0.550

Appendix

Table 16 Effect of hole diameter of the gas distributor on the removal rate of
copper, pH=4, Co=25 mg/l, SDS=350 mg/l, Q=250 ml/min, Ethanol=1%.

C/Co
Time (min) do=0.5mm do=1mm
5 0.698 0.725
10 0.545 0.628
15 0.449 0.520
20 0.378 0.467
25 0.312 0.383
30 0.279 0.329

35 0.259 0.320
40 0.249 0.317