REMOVAL OF HEAVY METALS FROM

WASTEWATERS BY
ION FLOTATION

A Thesis Submitted to
the Graduate School of Engineering and Science of
İzmir Institute of Technology
in Partial Fulfillment of the Requirements for the Degree of

MASTER OF SCIENCE
in Environmental Engineering
(Environmental Pollution and Control)

by
Demet ERDOĞAN

June 2005
İZMİR
We approve the thesis of Demet ERDOĞAN
Date of Signature
........................................ 22.June.2005
Assoc. Prof. Hürriyet POLAT
Supervisor
Department of Chemistry
Izmir Institute of Technology

........................................ 22. June.2005

Assoc. Prof. Serdar ÖZÇELİK
Co-Supervisor
Department of Chemistry
Izmir Institute of Technology

........................................ 22. June.2005

Assoc. Prof. Mehmet POLAT
Co-Supervisor
Department of Chemical Engineering
Izmir Institute of Technology

........................................ 22. June.2005

Prof. Dr. Devrim BALKÖSE
Department of Chemical Engineering
Izmir Institute of Technology

........................................ 22. June.2005

Assoc. Prof. Ahmet E. EROĞLU
Department of Chemistry
Izmir Institute of Technology

........................................ 22. June.2005

Asst. Prof. Aysun SOFUOĞLU
Head of Interdisciplinary
Environmental Engineering Program
Izmir Institute of Technology

Assoc. Prof. Semahat ÖZDEMİR

Head of The Graduate School
 ACKNOWLEDGEMENT

I would like to express my grateful thanks to my thesis supervisor, Assoc. Prof.

Dr. Hürriyet Polat and co-supervisors Assoc. Prof. Dr. Mehmet Polat and Assoc. Prof.
Dr. Serdar Özçelik for their guidance, understanding, motivations and endless support
during this study and preparation of this thesis.
I also would like to thank to Research Scientist Sinan Yılmaz at Chemistry
Department for his valuable help in AAS measurements.
Special thanks go to all friends, research assistants and technicians in İzmir
Institute of Technology for their helps and friendships.
I am also grateful to Leman Sütçü for her help during the study.
Finally, I would like to thank to my family for their support, continued patience,
encouragement and help throughout the course of my studies.
 ABSTRACT

In this study, ion flotation experiments were performed to investigate the

removal of heavy metals (copper, zinc, silver and chromium) from wastewaters.
Various parameters such as pH, surfactant and frother concentrations and airflow rate
values were tested to determine the optimum flotation conditions. Sodium dodecyl
sulfate and Hexadecyltrimethyl ammonium bromide were used as collectors. Ethanol /
MIBC were used as frothers.
For 10 mg/L initial concentrations of copper, zinc, silver and chromium (III), the
highest recoveries obtained were 90%, 71%, 73% and 97%, respectively. When the
initial concentration of metals increased the recovery decreased. This proves the
attachment of metal ions on surfactant molecules.
The presence of Na+, Mg2+, Ca2+ ions in solution reduced the recoveries in case
of all the metals since the presence of excess Na, Mg, Ca ions compete with metals and
the metal ions can not find enough surfactant molecules to attach to.
Selective flotation experiments were conducted in the presence of metal ion
mixture solutions. It was possible to separate copper and chromium from zinc and
silver, and also possible to separate chromium from zinc and copper and zinc from
copper and chromium under suitable conditions.
The classical first order equation fitted the results on flotation. Zinc and
chromium floated not only more in an amount but also floated faster than copper.
Surface tension measurements were conducted to investigate both the collector
surfactants and the frothers at air/water interface since air bubbles carry the surfactant-
metal ion complexes to the froth and separate from solution.

iv
 ÖZET

Bu çalışmada, ağır metallerin (bakır, çinko, gümüş, krom) iyon flotasyonu

kullanılarak atıksulardan uzaklaştırılması araştırılmıştır. Optimum flotasyon
koşullarının belirlenebilmesi için çeşitli pH, yüzey aktif madde, köpük sağlayıcı
derişimleri ve hava akış oranı test edilmiştir. Sodium dodecyl sulfate (SDS) ve
Hexadecyltrimethyl ammonium bromide (HTAB), yüzey aktif madde olarak, etanol ve
MIBC köpük sağlayıcı olarak kullanılmıştır.
Yapılan deneylerde 10 mg/L bakır, çinko, gümüş ve krom giderimi için sırasıyla
%90, %71, %73 ve %97’ lik verimler elde edildiği görülmüştür. Metallerin başlangıç
konsantrasyonları arttırıldığında yüzey aktif madde molekül sayısının yetersizliğinden
dolayı verimleri düşmektedir. Bu yüzey aktif madde molekülü ile metal iyonu
birleşiminin bir göstergesi olarak görülebilir.
Çözeltide sodyum, kalsiyum ve magnezyum iyonlarının bulunması bu iyonların
metal iyonlarıyla yarış içinde olmasından ve yeterli sayıda yüzey aktif madde molekülü
olmadığından flotasyon verimini düşürmektedir.
Koşullar ayarlandığında bakır ve kromun, gümüş ve çinkodan ayrılması
mümkündür. Yine koşullar ayarlandığında kromun çinko ve bakırdan oluşan çözeltiden
ayrılması da mümkündür. Bir diğer koşulda da çinko, bakır ve krom karışımından
oluşan çözeltiden ayrılmıştır.
Deneysel bulgular klasik birinci derece flotasyon modeline uymaktadır. Çinko
ve krom sadece miktar olarak değil yüzme hızı olarak da bakırdan daha hızlı
yüzmektedir.
Flotasyonda oluşan yüzey aktif madde-metal iyonu komplekslerini su yüzeyine
taşıyan hava kabarcıkları olduğundan, hem yüzey aktif madde toplayıcıların hem de
köpük yapıcıların hava/su ara yüzeyindeki etkilerini incelemek için yüzey gerilim
deneyleri gerçekleştirilmiştir.

v
 TABLE OF CONTENTS

LIST OF FIGURES ........................................................................................................ ix

LIST OF TABLES........................................................................................................... xi

CHAPTER 1. INTRODUCTION ..................................................................................... 1

1.1. Statement of the Pollution Problem ........................................................ 1
1.2. Health Effects ........ ................................................................................. 4
1.3. Common Methods Used to Remove Heavy Metals from Industrial
Wastewater............................................................................................. 4
1.3.1 Chemical Precipitation...................................................................... 4
1.3.2. Ion Exchange ................................................................................... 5
1.3.3. Reverse Osmosis.............................................................................. 5
1.3.4. Ultrafiltration ................................................................................... 6
1.3.5. Electrodialysis.................................................................................. 6
1.4. Scope of the Study .................................................................................. 6

CHAPTER 2. ION FLOTATION..................................................................................... 7

2.1. Dispersed Phases..................................................................................... 9
2.1.1. Metal ions ......................................................................................... 9
2.1.2. Surfactant molecules......................................................................... 9
2.1.3. Air Bubbles ..................................................................................... 12
2.1.3.1. Foams and Froths................................................................... 13
2.1.3.2. Theories of Foam and Froth Stability .................................... 13
2.2. Sub-Processes......... .............................................................................. 15
2.2.1. Collision.......................................................................................... 15
2.2.2. Attachment...................................................................................... 15
2.3. Effect of Surfactants on Various Sub-Processes................................... 16
2.3.1. Surfactants and Metal Ion / Surfactant Molecule Attachment........ 16
2.3.2. Surfactants Adsorbed at the Air/Water Interface............................ 17
2.4. Inorganic Agents, Activators, Depressants........................................... 17
vi
 2.5. pH of the System................................................................................... 18
2.6. Literature Survey .................................................................................. 18

CHAPTER 3. MATERIALS AND METHODS ............................................................ 23

3.1. Reagent.................. ............................................................................... 23
3.2. Apparatus............... ............................................................................... 24
3.2.1 Ion Flotation..................................................................................... 24
3.2.2. Atomic Absorption Spectrometry (AAS) ....................................... 26
3.2.3. Surface Tension Measurements ...................................................... 26

CHAPTER 4. RESULTS AND DISCUSSION.............................................................. 28

4.1. Surfactants............. ............................................................................... 28
4.2. Frothers................... .............................................................................. 30
4.3. Metals.................................................................................................... 33
4.3.1. Forms of Metal Ions in Water as a Function of pH ........................ 33
4.4. Ion Flotation Studies............................................................................. 36
4.4.1. Copper............................................................................................. 37
4.4.2. Zinc ................................................................................................. 43
4.4.3. Silver............................................................................................... 46
4.4.4. Chromium ....................................................................................... 50
4.5. Effect of Water Chemistry.................................................................... 52
4.5.1. pH of the solution ........................................................................... 52
4.5.1.1. Copper.................................................................................... 52
4.5.1.2. Zinc ........................................................................................ 53
4.5.1.3. Silver...................................................................................... 54
4.5.1.4. Chromium .............................................................................. 55
4.5.2. Ionic Strength.................................................................................. 56
4.6. Selective Flotation ................................................................................ 59
4.7. Kinetic Studies of Metals...................................................................... 61

CHAPTER 5. CONCLUSIONS ..................................................................................... 65

REFERENCES ............................................................................................................... 67

vii
APPENDICES
APPENDIX A. SURFACE TENSION........................................................................... 71
APPENDIX B. FORMS OF METALS IN WATER...................................................... 72
APPENDIX C. CALCULATION OF FLOTATION RESULTS................................... 80

viii
 LIST OF FIGURES

Figure Page
Figure 2.1. A Schematic Representation of Various Sub-Processes in Ion Flotation ...... 8
Figure 2.2a. No attachment in the Absence of Surfactant .............................................. 16
Figure 2.2b. Attachment in the Presence of Surfactant .................................................. 16
Figure 3.1. A schematic View of the Flotation Machine................................................ 25
Figure 4.1. Surface Tension of SDS solution at 25 oC ................................................... 29
Figure 4.2. Surface Tension of Ethanol / MIBC and SDS Solution. .............................. 31
Figure 4.3. Surface Tension of Ethanol / MIBC and SDS Solution with Metals. .......... 31
Figure 4.4. The Effect of Ethanol / MIBC Solution and Their Mixture of SDS with /
without Different Concentrations of Metals on Surface tension. ............. 32
Figure 4.5. Forms of Copper (10 mg/L) in Water as a Function of pH .......................... 34
Figure 4.6. Forms of Zinc (10 mg/L) in Water as a Function of pH .............................. 34
Figure 4.7. Forms of Silver (10 mg/L) in Water as a Function of pH ............................ 35
Figure 4.8. Forms of Chromium (10 mg/L) in Water as a Function of pH .................... 36
Figure 4.9. Effect of Ethanol Concentration on Copper Recovery as a Function.
of Time....................................................................................................... 38
Figure 4.10. Effect of Ethanol Concentration on Copper Recovery as a Function
of Time....................................................................................................... 38
Figure 4.11. Effect of Ethanol Concentration and Surfactant Concentration on Copper
Recovery as a Function of Time. ............................................................... 39
Figure 4.12. Effect of Airflow rate on Copper Recovery as a Function of Time. .......... 40
Figure 4.13. Copper Recovery as a Function of Water Recovery. ................................. 41
Figure 4.14. Copper Recovery as a Function of Water Recovery. ................................. 42
Figure 4.15. Copper Recovery as a Function of Water Recovery. ................................. 42
Figure 4.16. Effect of Ethanol Concentration and Surfactant Concentration on Zinc
Recovery as a Function of Time. ............................................................... 43
Figure 4.17. Zinc Recovery as a Function of Water Recovery....................................... 44
Figure 4.18. Zinc Recovery as a Function of Water Recovery....................................... 45
Figure 4.19. Zinc Recovery as a Function of Water Recovery....................................... 45

ix
Figure 4.20. Effect of MIBC Concentration and Surfactant Concentration on Silver
Recovery as a Function of Time. ............................................................... 47
Figure 4.21. Silver Recovery as a Function of Water Recovery. ................................... 48
Figure 4.22. Silver Recovery as a Function of Water Recovery. ................................... 48
Figure 4.23. Silver Recovery as a Function of Water Recovery. ................................... 49
Figure 4.24. Silver Recovery as a Function of Water Recovery. ................................... 49
Figure 4.25. Chromium Recovery as a Function of Water Recovery............................. 50
Figure 4.26. Chromium Recovery as a Function of Water Recovery............................. 51
Figure 4.27. Effect of Ethanol and Surfactant Concentrations on Chromium
Recovery as a Function of Time. ............................................................... 51
Figure 4.28. Copper Recovery as a Function of pH. ...................................................... 52
Figure 4.29. Zinc Recovery as a Function of pH............................................................ 53
Figure 4.30. Silver Recovery as a Function of pH.......................................................... 54
Figure 4.31. Chromium Recovery as a Function of pH.................................................. 55
Figure 4.32. Effect of Ionic Strength on Copper Recovery. ........................................... 57
Figure 4.33. Effect of Ionic Strength on Zinc Recovery. ............................................... 57
Figure 4.34. Effect of Ionic Strength on Silver Recovery. ............................................. 58
Figure 4.35. Effect of Ionic Strength on Chromium Recovery. ..................................... 59
Figure 4.36. Selectivity Results of Copper, Zinc, Silver and Chromium. ...................... 60
Figure 4.37. Selectivity Results of Copper, Zinc and Chromium................................... 60
Figure 4.38. Selectivity Results of Copper, Zinc and Chromium................................... 61
Figure 4.39. The Results of the Flotation Kinetics for Copper and Zinc ....................... 63
Figure 4.40. The Results of the Flotation Kinetics for Chromium. ................................ 63
Figure B.1. Forms of Copper (50 mg/L) in Water as a Function of pH ......................... 73
Figure B.2. Forms of Zinc (50 mg/L) in Water as a Function of pH.............................. 75
Figure B.3. Forms of Silver (100 mg/L) in Water as a Function of pH ......................... 76
Figure B.4. Forms of Chromium (50 mg/L) in Water as a Function of pH.................... 79

x
 LIST OF TABLES

Table Page
Table 1.1. Copper Levels Reported in Industrial Wastewaters ........................................ 2
Table 1.2. Zinc Levels Reported in Industrial Wastewaters............................................. 2
Table 1.3. Silver Levels Reported in Industrial Wastewaters........................................... 3
Table 1.4. Chromium Levels Reported in Industrial Wastewaters................................... 3
Table 1.5. Wastewater Standarts....................................................................................... 3
Table 1.6. Health Effects of Heavy Metals....................................................................... 4
Table 2.1. Physical Properties of Metal Ions .................................................................... 9
Table 3.1. Selected properties of the Surfactants Used in This Study............................ 23
Table 3.2. Structural formulas of the Surfactants Used in This Study ........................... 24
Table 3.3. Experimental Conditions for the Ion Flotation Tests .................................... 25
Table 4.1. Concentrations of Na, Ca, Mg in Tap Water Used in Studies....................... 56
Table 4.2. The First-Order Models with Distribution of Flotation Rate Constants Tested
for the Cu and Zn Recovery.......................................................................... 64
Table A.1. Surface Tension Values of Sodium Dodecyl Sulfate (SDS)......................... 71
Table B.1. Speciation Table of 10 mg/L Copper in Water as a Function of pH. ........... 72
Table B.2. Speciation Table of 50 mg/L Copper in Water as a Function of pH. ........... 73
Table B.3. Speciation Table of 10 mg/L Zinc in Water as a Function of pH. ................ 74
Table B.4. Speciation Table of 50 mg/L Zinc in Water as a Function of pH. ................ 75
Table B.5. Speciation Table of 100 mg/L Silver in Water as a Function of pH............. 76
Table B.6. Speciation Table of 10 mg/L Silver in Water as a Function of pH............... 77
Table B.7. Speciation Table of 10 mg/L Chromium in Water as a Function of pH. ...... 78
Table B.8. Speciation Table of 50 mg/L Chromium in Water as a Function of pH. ...... 79
Table C.1 Calculation of the Highest Recovery of Zinc................................................. 80
Table C.2 Calculation of the Highest Recovery of Silver. ............................................. 80
Table C.3 Calculation of the Highest Recovery of Chromium....................................... 81
Table C.4 Calculation of the Highest Recovery of Copper ............................................ 81

xi
 CHAPTER 1

INTRODUCTION

1.1. Statement of the Pollution Problem

Due to increase in the world population and development of industrial

applications, environmental pollution problem became important. Communities produce
both liquid and solid wastes. The liquid waste-wastewater- is essentially the water
supply of the community after it has been used in a variety of applications.The presence
of toxic and polluting heavy metals in wastewaters from industrial effluents, water
supplies and mine waters and their removal has received much attention in recent years.
The amount of heavy metals that industrial wastewaters often contain is considerable
and would endanger public health and the environment if discharged without adequate
treatment.
In Turkey , the situation is not so different from highly industrialized countries.
In recent years, heavy metal concentrations, besides other pollutants, have increased to
reach dangerous levels for living environment in many regions of Turkey. The
wastewater discharges such as those from the metal plating industries, are the main
sources of metal pollution and therefore the level of pollution is much higher in
industrialized regions.
Heavy metals are elements such as Cu (Copper), Zn (Zinc), Ag (Silver), Cr (III)
(Chromium), Hg (Mercury), Cd (Cadmium), Fe (Iron), Co (Cobalt), As (Arsenic) which
are usually associated with toxicity. Among them only Cu, Zn, Ag and Cr will be
studied in this thesis. Copper is present in wastewaters of most industries such as metal
cleaning and plating baths, mining and acid mine drainage, petroleum refining, paint
and pigment manufacturing, motor vehicle and aircraft plating and finishing, copper ore
extraction in different ranges from 0.12 mg/L to 183 mg/L (Table 1.1). Industries which
contain significant levels of zinc include steel works with galvanizing lines, zinc
plating, acid mine drainage, plating and metal processing, paint and manufacturing,
textile dying, pigment manufacturing. In waste waters of industries, zinc values were
reported to range from 0.01 mg/L to 1,702 mg/L (Table 1.2.). Silver is a naturally
occurring metal that is extensively utilized in the photographic and imaging industry, as
1
well as in electronics and electrical applications and other lesser uses. It is known to be
discharged to the environment from its industrial applications, and this leads to the
possibility for exposure to aquatic organism (Purcell et al. 1997). Silver values were
reported to range from 100 mg/Lto 300 g/L (Table 1.3.) in such waste waters.
Chromium is considered as a highly toxic water pollutant. Chemical industries, leather,
paint and cement industries produce high content chromium wastes that are ranged from
0.01 to 30 mg/L (Table 1.4.).

Table 1.1. Copper Levels Reported in Industrial Wastewaters

(Source: 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
Acid mine drainage 0.12-128
Petroleum refining 0.0-1.4
Copper ore extraction 0.28-20

Table 1.2. Zinc Levels Reported in Industrial Wastewaters

(Source: Metcalf and Eddy 2003)

Industrial Source Zinc Concentration (mg/L)

Metal processing 0.2-1,000
Zinc plating 2-1,050
Paint manufacturing 0.3-77.4
Textile dyeing 2-6
Pigment manufacturing 0-1,702
Steel works 2.1-1,210

2
 Table 1.3. Silver Levels Reported in Industrial Wastewaters
(Source: WEB_1 2003)

Industrial Source Silver Concentration (mg/L)

Photographic manufacturing 100-260000
Steam wells 100-300000
Oil well brines 10-100

Table 1.4. Chromium Levels Reported in Industrial Wastewaters

(Source: Metcalf and Eddy 2003)

Industrial Source Chromium Concentration

(mg/L)
Chemical industries 1.1-17.7
Leather industries 1.7-55
Paint industries 2.5-30

In order to reduce the pollution problem in environment that is caused by these

heavy metals, their concentrations must be reduced before discharging to obey the
wastewater standarts listed in Table 1.5. So, an effective treatment process must be
applied.

Table 1.5. Wastewater Standarts

( Source: WEB_2 2004)

Metal Ion Maximum Allowable

Value, (mg/L)*
Copper 1
Zinc 5
Silver 0.2-2.0µg/L
Chromium 0.5

3
1.2. Health Effects

Heavy metals are released into the environment by activities of people and high
levels of these metals constitute a great risk for the aquatic ecosystem and human.
Health effects of Cu, Zn, Ag, and Cr are listed in Table 1.6.

Table 1.6. Health Effects of Heavy Metals

(Source: WEB_3 2003)

Copper nausea,vomiting,abdominal pain, damage

the liver and kidneys.
Zinc stomach cramps,nausea, vomiting, anemia,
pancreas damage.
Silver nausea, vomiting, skin irritation, damage
the liver, kidney, eyes, lung and brain
Chromium irritation to the nose, cause stomach upsets
and ulcers, kidney and liver damage.

1.3. Common Methods Used to Remove Heavy Metals from Industrial

Wastewaters

Methods such as chemical precipitation, solvent extraction, reverse osmosis,

ultrafiltration, electrodialysis, ion exchange are used commonly to remove heavy metals
from wastewater to day. The summary of these methods will be given in the following
paragraphs.

1.3.1 Chemical Precipitation

Chemical precipitation involves the addition of chemicals to alter the physical

state of dissolved and suspended solids and facilitate their removal by sedimentation.
Chemical precipitation is employed for most of the metals. Common precipitants
include hydroxide (OH)- and sulfide (S2-). Metals are precipitated commonly as metal
hydroxides through the addition of lime or caustic to a pH of minimum solubility. In
practice, the minimum achievable residual metal concentrations are also dependent on
the nature and concentration of the organic matter in the wastewater as well as the
temperature. However, this method is inappropriate for large solution volumes with
4
very low concentrations of metal ions. Precipitating hydrous oxides of the metals with
lime and soda (NaOH) is used in removal of heavy metals. The cost of most of the
coagulants, chemical and polyelectrolytes used for precipitation of the metals, in the
conventional methods, makes the process economically unattractive. Precipitation
generates large amounts of sludge , which is costly to dispose of and often hazardous
besides requiring long settling times despite the use of coagulants (Metcalf and Eddy
2003).

1.3.2. Ion Exchange

Ion exchange is a unit process in which ions of a given species are displaced
from an insoluble exchange material by ions of a different species in solution. Materials
used for the exchange of metals include zeolites, weak and strong anion and cation
resins, chelating resins. Ion exchange processes are highly pH-dependent. Solution pH
has a significant impact on the metal species present and the interaction between
exchanging ions and the resin. Operating and wastewater conditions determine
selectivity of resin, pH, temperature, other ionic species and chemical background. The
presence of oxidants, particles, solvents and polymers may affect the performance of
ion exchange resins (Eckenfelder 2000).

1.3.3. Reverse Osmosis

Reverse osmosis is used for the removal of dissolved constituents from

wastewater remaining after advanced treatment. When two solutions having different
solute concentrations are separated by a semipermeable membrane, a difference in
chemical potential will exist across the membrane. Water will tend to diffuse through
the membrane from the lower concentration side to the higher concentration side. In a
system having a finite volume, flow continues until the pressure difference balances the
chemical potential difference. This balancing pressure difference is termed the osmotic
pressure and is a function of the solute characteristics and concentration and
temperature. If a pressure gradient opposite in direction and greater than the osmotic
pressure is imposed across the membrane, flow from the more concentrated to the less
concentrated region will occur and is termed reverse osmosis ( Metcalf and Eddy 2003).
Reverse osmosis has been proposed for treatment for recovery of heavy metals. To
protect the reverse osmosis membranes, feed solution pH must be adjusted. Reverse

5
osmosis alone will not achieve complete recovery and reuse of the solutions.
Pretreatment required prior to the reverse osmosis unit includes equalization, media
filtration, pH adjustment and antiprecipitant additions.

1.3.4. Ultrafiltration

Ultrafiltration technologies can be used in a variety of ways in wastewater

treatment and water reuse systems. Ultrafiltration can reduce the amount of treatment
chemicals, has smaller space requirements, and reduce labor requirements. On the
contrary in this method uses more electricity, may need pretreatment, requires
replacement of membranes. ( Eckenfelder 2000 ).

1.3.5. Electrodialysis

In the elecrodialysis process, ionic components of a solution are separated

through the use of semipermeable ion-selective membranes. This process may be
operated in either a continuous or a batch mode. Problems associated with the
electrodialysis process for wastewater renovation include chemical precipitation of salts
with low solubility on the membrane surface. To reduce the membrane fouling,
activated carbon pretreatment, posibbly preceded by chemical precipitation and some
form of multimedia filtration may be necessary (Metcalf and Edddy 2003). The
electrolytic process has not been widely utilized in full-scale treatment of metal wastes.

1.4. Scope of the Study

The scope of this study was to investigate the removal of heavy metals
especially copper, zinc, silver and chromium which are highly toxic metals, from
industrial wastewaters by ion flotation. The objective of this investigation is to establish
the optimum ion flotation conditions in terms of pH, surfactant concentrations, ethanol
concentrations, airflow rate values in order to remove metals effectively and selectively
from wastewaters.

6
 CHAPTER 2

ION FLOTATION

For 100 years, the separation and preconcentration bubble methods called
flotation has been used in mining and metallurgical industry to operate valuable
minerals from natural resources. Apart from mining aims, these techniques have found
great application for separating and removing many kinds of harmful impurities from
different polluted water systems. Today, there are several attempts to apply flotation
(Pavloska 2003).
There are many differences between an industrial flotation processes, where the
materials floated are the relative massive grains of ores and flotation as an analytical
method, where the particles are invisible ions or molecules. However for both
procedures the same principles and laws are valid (Caballero 1990).
Ion flotation is a comparatively novel separation technology, first described by
Sebba in 1959, for recovering and removing metal ions from dilute aqeous solutions
(Bernasconi 1998 ; Jdid and Blazy 1990 ; Matis and Mavros 1991 ; Tessele 1998). This
process involves the removal of surface inactive ion species from aqeous solution by
adding the proper long chain surface active agent of opposite charge to the ion to be
separeated. A surface active reagent , known as collector, is added to the solution to be
treated and adsorbs at the solution – gas interface. After the subsequent passage of gas
bubbles through the solution, surfactant and ions are accumulated at the gas/liquid
interfaces and are carried into a foam or froth, rising above the solution. The froth is
swept from the top of the flotation cell. Appropriate surfactants prevent bubble rupture
and promote the formation of a foam (Zouboulis 1995).
Ion flotation is a complex process which occur in a multi-component, multi-
phase system. A schematic representation of various sub-processes which take place
during flotation is given in Figure 2.1. The figure shows the three dispersed phases in
the flotation cell, namely, metal ions, surfactant molecules and air bubbles, and their
interactions with each other. Water is considered to be the continuous medium in which
the interactions take place and is therefore not shown in Figure 2.1. It is also assumed
that these interactions take place under an unchanging set of hydrodynamic conditions.

7
Chemical and physical properties of each dispersed phase affect the overall flotation
response through various sub-processes. A detailed discussion is presented in the
following paragraphs.

t n Metal Ions

Me Co
ion cta

tal
ent
llis rfa

At

Ion lision
Co / Su

hm

ta

l
chm

/A
tac
Ion

ir B
At

ent
tal

FLOTATION

ub
Me

Attachment le b

Surfactant Air
Molecules Bubbles
Surfactant / Air Bubble
Collision

Figure 2.1. A Schematic Representation of Various Sub-Processes in Ion Flotation

8
2.1. Dispersed Phases

2.1.1. Metal ions

In aqeous solution free metal ions are complexed with water and these are said
to be hydrated. The interaction of hydrated metal ions with acids and bases is a ligand
exchange reaction which is called hydrolysis. It describes general reaction in which a
proton is transferred from an acid to water or from water to base. This type of reaction
which involves hydrated metal cations as the proton-donors or acids occurs readily. The
hydrolysis of metal ions is a stepwise replacement of coordinated molecules of water of
hydration by hydroxyl ions. This replacement forms by the transfer of protons from
waters of hydration to free water molecules to occur an hydronium ion. The hydrolysis
reactions depicted as acid-base (proton transfer) reactions. Because of this, the pH of the
system will influence the distribution of the various species. In general, the percentage
of the hydrolyzed species increases as the pH increases, while the concentration of a
conjugate base would increase if the pH of a solution containing its conjugate acid were
raised. All heavy metal ions, used in this study, form complexes with numerous ligands
that are present in water and wastewater. Forms of these metal ions in aqeous solution
will be shown and explained with details in Chapter IV. And now physical properties of
metal ions need to be known that understanding these ions. The physical properties of
metal ions, that are copper, zinc, silver and chromium, are given in Table 2.1.
(Greenwood 2003).
Table 2.1. Physical Properties of Metal Ions
(Source: Greenwood 2003)

Properties Copper Zinc Silver Chromium

Atomic weight 63.55 65.39 107.87 51.99
Electronegativity 1.9 1.6 1.9 1.6
Metal radius
128 134 144 128
(12-coordinate) / pm
Effective ionic radius
73 74 94 61.5
(6-coordinate)/pm
Melting point (oC) 1083 420 961 1900
Boiling point (oC) 2570 907 2155 2690
Density (20oC) g/cm3 8.95 7.14 10.49 7.14

9
2.1.2. Surfactant Molecules

The term soap is applied to the sodium or potassium salts of long – chain fatty
acids that are but one example of a general class of substances called amphiphiles.
Those are substances whose molecules consist of two well-defined regions : one which
is oil-soluble ( hydrophobic, lipophilic..) and one which is water soluble ( hydrophilic).
The hydrophobic part is non-polar and usually consists of aliphatic or aromatic
hydrocarbon residues. The hydrophobic character is not much affected by introducing
halogens and similar groups (Laughlin 1981). The hydrophilic part consist of polar
groups which can interact strongly with water (especially hydroxyl, carboxyl and ionic
groups). Typical examples are;

C19H42NBr Æ Hexadecyltrimethyl Ammonium Bromide

CH3(CH2)11O.SO2O-Na+ Æ Sodium Dodecyl Sulphate

CH3(CH2)13.O.SO2O-Na+ Æ Sodium Tetradecyl Sulphate

The most significant characteristic of this type amphiphile tends to adsorb very
strongly at the interface between air and water, thus the hydrophobic part of the
molecule can escape from the aqeous environment when the hydrophilic head group can
remain in the water. Such substances are said to be strongly surface active because they
lower the surface tension. Therefore they make the formation of new surface easier and
are widely used as foaming and dispersing agent (Hunter 2001).
Depending on the nature of hydrophilic group, surfactants are classified as
(Rosen 1989) ;
• Anionic : The surface active portion of the molecule bears a negative charge.
• Cationic : The surface active portion of the molecule bears a positive charge.
• Zwitterionic : Both positive and negative charges may be present in the surface-
active portion.
• Nonionic : The surface active portion bears no appearent ionic charge.

For surfactants having not only hydrophilic part but also hydrophobic part
causes some effects such as ;

10
 Increase in the length of the hydrophobic group decreases the solubility of the
surfactant in water and increases its solubility in organic solvents, increases the
tendency of the surfactant to adsorb at an interface or to form micelles, increases the
melting point of the surfactant and sensitivity of the surfactant, if it is ionic, to
precipitation from water by counterions (Rosen 1989).
At very low concentrations (<10-4 M) many surfactants are soluble in water to
form simple solutions. Some of the molecules will also be adsorbed at the surfaces of
the solution. As the concentration rises adsorption becomes stronger until saturation is
reached when the molecules are packed close together with strong lateral interactions
occuring between the hydrophobic chains. At this point formation of micelle is
important. These are structures in which the hydrophobic portions of the surfactant
molecule associate together to form regions. The hydrophilic groups remain on the outer
surface to maximize their interaction with the water and the oppositely charged ions
(called counter ions). A significant fraction of the counterions remains strongly bound
to the head groups so that the repulsive force between those groups is reduced. The
structure of the micelle depends upon the temperature and concentration but also on the
details of the molecular structure : size of head group, length, number of hydrocarbon
chains, presence of branches, etc. (Hunter 2001).
The concentration at which micelles first form in the solution is called the
critical micellization concentration (c.m.c.). Micellization is an alternative mechanism
to adsorption at the water, thereby reducing the free energy of the system. It’s marked
by quite sharp changes in slope when various transport and equilibrium properties are
plotted against concentration. The long chain fatty acid soaps and simple detergents like
sodium dodecyl sulphate (SDS) initially form micelles that are spherical in shape. As
the surfactant concentration is increased above the c.m.c., the initially spherical micelles
become more distorted in shape, forming cylindrical rods or flattened discs (Hunter
2001).
For surfactants with a single straight hydrocarbon chain, the c.m.c. is related to
the number of carbon atoms in the chain.
One of the most surprising things about micellization is the very weak
temperature and pressure dependence of the c.m.c., considering that is an association
process (Lindman and Wennerström 1980). Raising the temperature has a quite
different effect on ionic and non-ionic surfactants. For ionics, there is a temperature
below which the solubility is low and solution appears to contain no micelles. Above
11
this temperature micelle formation becomes possible and there is an increase in
solubility of the surfactant. It is significant that surfactants are less effective below this
point.
Foam height generally increases with increase in surfactant concentration below
the c.m.c. until the c.m.c. is reached, foam height reaches a maximum value somewhat
above the c.m.c. The lower c.m.c., the more efficient the surfactant as a foamer.
Surfactants with longer hydrophobic groups are more efficient, but not necessarily more
effective, foaming agents. The effectiveness of a surfactant as a foaming agent appears
to depend on both its effectiveness in reducing the surface tension of solution and on
the magnitude of its intermolecular cohesive forces. The lower the surface tension of the
aqeous solution the greater appears to be the volume of foam of the same average
bubble size produced (Rosen 1969).

2.1.3. Air Bubbles

Air bubbles are introduced into the system to capture and carry hydrophobic
particles to the froth phase leaving hydrophilic ones selectively behind. In a typical
flotation cell the bubble size ranges from about 0.5 to 1.0 mm. When bubble size is
reduced, the number of bubbles in the system will increase for the same volumetric air
flow rate and should result in higher flotation rates. Frothers are usually employed to
prevent bubble coalescence and to increase the stability of the froth.
Bubbles can be generated in liquids by several different methods, for example;
• An increase in temperature to cause boiling at first, dissolved gases are
released, and ultimately vapour- filled bubbles are generated.
• A decrease in pressure to cause precipitation of bubbles.
• A mechanical agitation to cause gas entrapment.
• An injection of gas through an orifice or a porous membrane.
Once formed within a pure liquid, bubbles tend to coalesce ( to reduce the extent
of total surface area and thus the overall amount of free energy in the system) and (if
free) to rise in the liquid under the effect of buoyancy. Both the coalescence by surface
active impurities and the rise by attachment to a hydrophobic surface (Leja 1982).

12
2.1.3.1. Foams and Froths

When two bubbles come in contact with each other, liquid film between them
thins and breaks, causing bubbles to coalesce, unless excess surfactant is present at their
interfaces or the time of contact is too short. Bubble coalescence can be studied either
on two bubbles grown in solution by blowing compressed gas through a fine glass frit
(Sagert 1976).
When coalescence of bubbles formed in a liquid does not take place in fractions
of seconds, the bubbles rise to the surface and aggregate, forming a foam or a froth. The
terms foam and froth are sometimes used interchangeably; however, the imperfectly
drained liquid - bubble systems, generally unstable, are called foams, better drained
bubble systems are referred to as froths. Two phase froths are obtained with solutions of
ionized surfactants (Leja 1982).
There is a strong correlation between the viscosity of liquid and the stability of
foam. The more viscous the liquid into which the bubbles are injected, the slower is the
drainage of liquid from layers between the bubbles. In pure viscous liquids of different
surface tension showed that the rate of collapse was the same for all systems when their
viscosities were made equal by keeping each system at an appropriate temperature. The
values of surface tension wasn’t a critical factor in these foams (Clift et al. 1978).
Foams and froths are thermodynamically unstable, since the free energy of the
system decreases when they collapse. The lifetime of foam or froth depends on a
number of surface chemical and physical parameters, namely concentration of
surfactants, surface viscosity and transport, all of these, in turn ,are determined by the
molecular structure of the surfactant used and interactions between surfactants, solutes
and water molecules.

2.1.3.2. Theories of Foam and Froth Stability

The most important factor in the formation of foam is the presence of a

surfactant at the liquid/gas interface. The effectiveness of different surfactants is
assessed by measuring the foam lifetime (stability). This is done by several methods,
such as; When air is injected at a given rate into a solution, or mechanical, when the
solution is agitated with a propeller, etc. In each instance, the air is dispersed for a given
length of time, at the end of which the volume of froth is estimated and its decay with
time measured (Leja 1982).
13
 A significant feature of all frothers used in flotation systems is their nonionic
polar group. Characteristic of the better-acting frothers is the nonadlineating structure of
their nonpolar groups. All n-alkyl hydrocarbon chains of surfactants readily develop
multiple van der waals bonds, that is, become adlineated. This adlineation occurs, if the
polar groups associated with the chains aren’t much larger than the cross section of the
hydrocarbon chain itself. The bubbles themselves are always charged, whether in pure
water, in solutions of organic electrolytes, or in solutions of surfactants. Owing to a
preferential adsorption of OH-, there is a definite pH dependence of their charge,
whether in water or in nonionic surfactant solutions. In view of these features, there is a
high probability that similarly charged hydrophobic ions and bubbles will be colliding
with each other in a flotation cell (Jones et al. 1984).
The main role of frother-acting surfactant in flotation is to provide means of
replacing repulsive forces, whenever necessary, with attraction, owing to the ability of
such surfactant molecules to align their dipoles appropriately at the moment of ion-
bubble collision.
It is from ability to align their dipoles that nonionic surfactants with
nonadlineating hydrocarbon groups prove themselves the better frothers. The interaction
with the collector species is beneficial, but not always so. When it is so strong that it
prevents dipole realignment, collisions may result in no attachment (the respective polar
groups are then lockes together ). On the other hand, even a strong interaction between
collector and frother species may allow an attachment to take place but no froth is
generated because the nonpolar groups of the reacting frother-collector molecules form
an adlineated film. Surfactants with charged polar groups may act as frothers but only in
situations under which ions are oppositely charged with respect to the charge on the
bubbles. Such conditions are not likely to be met in practice over an extensive range of
concentrations or pH. It is ,however, that some charged surfactants are capable of acting
in a dual capacity as a collector and a frother by virtue of providing a sufficient quantity
of neutral products through reactions with counterions (Leja 1982).

14
2.2. Sub-Processes

The three dispersed phases interact through collision, attachment and

detachment sub-processes which could occur simultaneously or sequentially depending
on the environmental conditions. The physical and chemical properties of each
dispersed phase determine the outcome of each sub-process, hence, the flotation
response. In the following paragraphs a detailed discussion of these interactions is
presented.

2.2.1. Collision

The major physical properties which influence the collisions probability between
the three dispersed phases are the size, number, density and shape. Efficiency of
collision may be defined as the ratio of particles (metal ions, surfactant molecules or air
bubbles) colliding with a given body to those flowing across the projected collision
cross sectional area of that body. A successful collision only means that the two bodies
have approached within a certain distance and may, or may not, result in attachment.

2.2.2. Attachment

A successful attachment between the two members of any of the dispersed

phases given in Figure 2.1 requires that the water film between them should drain out
within the time frame of collision. Probability of adhesion could be defined as the
fraction of the colliding particles which would adhere to the body upon which they
impact. Similar to the collision probability, a separate adhesion probability may be
defined for each surfactant molecule/metal ion, surfactant molecule/air bubble and
metal ion/air bubble pairs. While the collision probability is mainly affected by the
physical properties of the particles, the adhesion probability is determined by both the
physical and chemical properties of the impacting particles.
Attachment or coalescence sub-processes between similar dispersed phases,
bubble/bubble, may be detrimental to flotation since the dispersed forms of this phase
are required for maximum in flotation.

15
2.3. Effect of Surfactants on Various Sub-Processes

A variety of reagents might be used to modify the surface properties of the

dispersed phases given in Figure 2.1. The reagents capture metal ions and also adsorb at
air/water interface and influence the outcome of the sub-processes, hence, flotation. As
a result the role of surfactants in flotation is very complex. The mechanism and quantity
of adsorption at air/water interface will be determined by factors such as surfactant type,
concentration and conditioning.

2.3.1. Surfactants and Metal Ion / Surfactant Molecule Attachment

The key to flotability of chemical species is hydrophobicity. Substances are

rendered hydrophobic by addition of the suitable collector, in which polar groups are
eliminated by reaction leaving non-polar groups exposed to solution. These groups can
be adsorbed on the liquid / gas interface (Matis et al. 1995).
The anionic surfactant, with its negative – charged part, adsorbs onto 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
onto the hydrocarbon chain and the separation of the ions from the liquid phase. Figure.
2.2a shows no attachment of a metal ion on air bubble in the absence of a surfactant,
2.2b shows an attachment of a metal ion in the presence of a surfactant.

= + C12H25
SO 4----Na

Metal ion
Air bubble
Metal ion
(positively charged) + Air bubble
+

Figure 2.2a. No attachment in the Figure 2.2b. Attachment in the

absence of surfactant (SDS) presence of surfactant

16
 The quantity of collector used in ion flotation is also important. Usually small
excess of collector is added to have maximum removal of metallic ions in solution.
Excessive surfactant should be avoided not only due to higher cost, but also because of
other effects, such as large foam losses and the potential toxicity of residuals amounts of
collector in the effluent.

2.3.2. Surfactants Adsorbed at the Air/Water Interface

Adsorption of a surfactant at the air/water interface results in finer bubbles and

a stable froth and therefore affects the collision and adhesion sub-processes. This is one
of the most frequent use of water soluble surfactants in flotation (frothers). Some
commonly used frothers in flotation are MIBC (methyl isobutyl carbinol), ethanol,
methyl ethers (e.g., Dowfroth 250), polypropylene glycol, dodecylamine. Many
commercial frothers are known to have both frothing and collecting properties. The
creation of a finer bubble size distribution through changes in dynamic surface tension
is also a very important result of frother addition. However, similar to collector
chemicals, higher concentrations of frothers shoul be avoided (Duyvesteyn 1993;
Alexandrova 1996).

2.4. Inorganic Agents, Activators, Depressants

The purpose of making an addition of any reagent to a flotation system is to

improve floatability of the desired ion at the desired moment to achieve selectivity of
separation. The additivies are grouped under different headings, depending on their
action. Thus, these additivies, inorganic or organic in nature, which,
• Control the pH of the system
• Regulate the oxidation states of ions in solution of surfactants used as collectors
• Control the concentration of metallic ions in solution and at interfaces through
precipitation or complexing with HS-, CN-, OH-, etc...
Additivies which are more specific in their action are called activators. Reagents
which have a specific opposite effect to activators are called depressants. It is obvious
that the same chemical species may act as a regulatory agent or an activator, or a
depressant, depending on the character of the flotation system. At the same time,
depending on the concentration, it is reducing agent and a highly selective charge
density regulator (Leja 1982).
17
2.5. pH of the System

The type of additive used to control the ph is often of paramount significance.

Although an acidic pH can be obtained by HCl, H2SO4, HNO3, etc... the price is not the
criteria to follow in deciding which additive to use, since the side effects of Cl-, SO42-,
NO3- ions may play a very significant role in some systems. The solution pH
determines the extend of hydrolysis of surfactants. This, in turn, either helps or hinders
the adsorption of the surfactant at the various ionized liquid interfaces, contributing to
greater or lesser selectivity of flotation (Scorzelli 1999).
Metal cations exist in aqeous solutions primarily as complexes of H2O
molecules and OH- ions; when the oxidation state of the metal cation is higher, in
addition to hydroxyl complexes some OXO ( containing O2- as a ligand ) complexes
appear in the pH range 4-10. Because of the limited pH range of aqeous solutions, not
all of the possible metal complexes can exist as an ionic hydroxyl or OXO complexes.
Polymerization of hydrolysis species results in the formation of colloidal hydroxyl
polymers. These species are bonded through OH bridges or through O bridges. The
extent of hydrolysis depends on the pH and total concentration of metallic ion. Two
ways of graphing the distribution of complexes can be drawn, either as a percent mole
fraction of individual species at each pH or as relative intermediate S curves. A third
way of graphing the relationship between pH and hydrolysis species can be plotted with
the log concentration of each hydrolysis versus the pH for a thermodynamic equilibrium
between species. When the solution become oversaturated with respect to Mn+(OH)n -
depending on the kinetics of precipitation- a colloidal hydroxide is present in addition to
the hydrated complexes in solution (Leja 1982).
When simplified systems containing individual ions in solution are tested in
collector at different pH, the comparison of results may indicate definite differentiation
in collector adsorption. This would suggest that flotation of ions should occur in
different pH ranges, giving rise to selectivity controlled by pH.

2.6. Literature Survey

Charewicz et al. 1999 examined the batch flotation of zinc (II) and silver (I) ions
from dilute aqeous solutions with sodium dodecyl sulphate and ammonium
tetradecylsulfonate as anionic surfactants and with cetylpyridinium chloride as a
cationic surfactant. Also, they studied the effect of inorganic ligands (thiosulphates,
18
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 acidic aqeous solutions with
anionic surfactants since Zn2+ 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.
A thermodynamic approach was investigated to model the removal of cupric ion
from (sodium dodecyl sulphate) SDS-Cu, (sodium tetradecylsulphate) 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 anayltical 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.
Liu et al. 2000 developed theoretical models to find the selectivity coefficients
for Ca2+ / Cu2+ and Pb2+ / Cu2+ in ion flotation by using SDS as the collector. Also, they
studied to improve surface tension model using surface tension data for the metal-SDS
ion flotation systems. Other important thing for this study was to calculate theoretically
the dehydration parameter and dehydration Gibbs free energy using geometric
considerations. Then this incorporated into a Grahame adsorption equation to derive a
selectivity coefficient for two metal ions at the solution-vapour interface. Finally they
concluded the dehydration model gave a good prediction of the selectivity coefficients
this was not the same in the surface tension model.
Zouboulis et al. 1995 investigated the recovery of silver from dilute aqeous
solutions containing complexing 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 synthethic solutions. Experiments were
performed using cationic surfactant dodecylamine (DA), as a frother ethanol. High
recoveries of silver from aqeous solutions containing thiosulphates and optimum
conditions for the recovery of silver were obtained.
Doyle et al. 2003 observed the fundamental characteristics of ion flotation in the
context of their implications for commercial applications. These characteristics included
the kinetics of metal ion removal, the ability to recover metal values from the foam

19
product, the ability to separate ions selectively from mixed solutions and a comparison
of the performance of ion flotation with other separation methods.
Girek et al. 2004 studied that the competitive ion flotation of Cu2+ , Zn2+ , Cd2+
cations from diluted aqeous solutions. Firstly, they prepared β – cyclodextrin (β-CD)
polymer. The chemical structure of the polymers were determined using high
performance size exclusion chromatography (HPSEC) with refractive index (RI)
detector and H-NMR spectrocopy. They obtained results of ion flotation of copper (II)
by using nonylphenol polyoxyethyl glycol ether as an non-ionic surfactant and β-CD
polymers as complexation agent, showed the removal of metal decreases with higher
molecular mass of β-CD polymers.
Pavloska et al. 2003 examined that selective separation of impurities contained
in aragonite (CaCO3) before their determination by AAS was performed by flotation.
Preliminary tests were performed in order to find suitable optimal concentration of
aragonite solution for flotation. They found the detection limit of AAS method and
determined by electrothermal atomic absorption spectrometry (ETAAS). They proved
in this study that flotation could solve very important problems characteristic of ETAAS
analysis of trace element in minerals resulting of matrix interferences.
Doyle et al. 2003 reported that the effect of a neutral chelating ligand,
triethylenetetraamine (Trien), on the ability to separate copper (II) and calcium (II) ions
and compared the ion flotation behaviour of Cu2+ and Ni2+ aquo-ions with the behaviour
of Cu- Trien2+ and Ni-Trien2+ complexes. In experiments, SDS was used as the
collector. They concluded that the copper was removed preferentially, whereas in the
absence of Trien, the calcium was removed. Trien was shown markedly increase the
removal rates of Cu2+, Ni2+ 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.
The removal of Cd (II) using SDS as a collector was studied by Scorzelli et al.
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 reduce in floatability which was related to the adsorption of SDS at
interface liquid-gas. The best recovery with a dry foam was obtained as 88,2% in the
presence of SDS.
20
 The competitive ion flotation of Zn (II) and Cd (II) ions from diluted aqeous
solutions by the anionic surfactant (sodium dodecylbenzenesulfonate) in the presence of
4- thioazolidinone derivatives was studied by Kozlowski et al. 2002. The effect of
structural evaluation of 4-thioazolidinone derivatives was also discussed. In this study
they concluded that the removal of both metals decreased with higher concentration of
4-thiazolidinones derivatives. The removal of metal ions in competitive ion flotation
was found to increase with stability for Cd (II) complexes with tautometric ligands.
Zouboulis et al. 2003 investigated that the removal of zinc and chromium ions
from aqeous 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 examined as alternative collectors for flotation
methods. The conclusion was drawn from experimental data; biosurfactants effectively
removed sorbent material and presented. Both biosurfactants removed chromium ions
after sorption studies. Surfactin was proved to be an effective surfactant for the removal
of zinc ions after sorption process.
Competitive flotation of zinc and cadmium ions from dilute solutions by side-
armed lariat ether-type derivatives of diphosphaza-16-crown-6 ethers in the presence of
nonylphenol nonyethylene glycol ether as the non-ionic foaming agent was investigated
by Ulewicz et al. 2003. They reported effects of structural modification of PNP-lariat
ethers upon the efficiency and selectivity of ion flotation of zinc and cadmium ions. The
influence of Li+ and Na+ on Cd2+ ion flotation removal was also studied. They found the
removal of Cd2+ increased with increasing of pH values. The efficiency of cadmium
flotation decreased with alkali metal cations concentrations increased.
Lazaridis et al. 2004 was investigated the recovery of copper ions from
wastewaters. 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 aqeous
solutions, using SDS as anionic collector and ethanol as a frother was investigated by
Medina et al. 2004. The adequate experimental conditions were obtained through
precipitate flotation such as SDS and ethanol concentration and gas flow rate. They

21
studied the results led to a first order model for the removal of chromium III by
precipitate flotation.
Matis et al. 2005 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 influnce on membrane performance.
A study concerning the kinetics of Cu2+aq ions separation by precipitate flotation
using alkylamine type (laurylamine) and alkylammonium salt
(lauryltrimethylammonium chloride) as cationic collectors and sodium laurysulphate
and sodium oleate as anionic collectors was presented by Stoica et al. 2003. Obtained
data were used to verify the classical first order model and three 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.

22
 CHAPTER 3

MATERIALS AND METHODS

3.1. Reagents

Sodium dodecyl sulfate (sodium lauryl sulfate) (SDS, 99%) from Sigma and
Hexadecyltrimethyl ammoniumbromide from Sigma were used as collectors. A
summary of these surfactants with some common characteristics are given in Table 3.1,
while their chemical structures are presented in Table 3.2. Ethanol (C2H5OH ) from
Carlo Erba and methyl isobutyl carbinol (MIBC) from Merck were used as frothers.
Copper nitrate (Cu(NO3)2) from Sigma, zinc nitrate hexahydrate (N2O6Zn, 98%) from
Aldrich, chromium (III) chloride hexahydrate (CrCl3.6H2O, 99%) from Sigma and
silver nitrate (AgNO3) from Carlo Erba were used to prepare working solutions. The
solution pH was adjusted using caustic soda (NaOH) and hydrochloric acid (HCl).
Double distilled water which was passed through Barnstead Easypure UV- Compact
ultrapure water system (18.3 ohm) was used to prepare the stock solutions.

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

Hydrophobic Hydrophilic Molecular C.M.C. x10–3

Commercial Name
Group Group Weight g/mol Moles/L
Anionic Surfactant
Na-Dodecyl
Dodecyl Sulfate 288 8.25a
Sulfate
Cationic Surfactant
Hexadecyltrimethyl Hexadecyl Ammonium 364.5 92.0b
ammoniumbromide

a. Mukerjee and Mysels, 1971

b. Czerniawski, 1966

23
 Table 3.2. Structural Formulas of the Surfactants Used in This Study

Sodium Dodecyl Sulfate Hexadecyltrimethyl ammoniumbromide

C12H25 O S O- ....Na+ CH3 N+ CH3

3.2. Apparatus

• pH- meter ORION 420A

• Ion Flotation Machine
• Surface Tension Measurement Instrument (Krüss, K10 ST)
• Atomic Absorption Spectrometry (AAS) (Perkin Elmer 2280)

3.2.1 Ion Flotation

Ion flotation experiments were conducted in a one liter cell using a Denver type
laboratory flotation machine. A schematic view of the flotation machine is given in
Figure 3.1. It consists of a cell where the separation takes place and impeller for mixing
the pulp and introducing the air. The experimental conditions for the ion flotation tests
were listed in Table 3.3. Solutions for ion flotation were prepared in a 1000ml
volumetric flask using appropriate amounts of metal ion with double distilled water to
make up 1 liter of solution. Then the solution pH was adjusted to a desired value using
HCl or NaOH solutions. The solution was stirred for approximetly 10 minutes to ensure
consistent mixing of reagents. The solution was then placed in the flotation cell. Firstly,
SDS solution was added in certain molar concentration values and mixed with the
solution that was in the flotation cell for a time period of 2 minutes. Appropriate
amounts of ethanol were added after applying SDS to the solution for 2 minutes. During
mixing of SDS, metal ion and ethanol solutions air was flowed through the sparger.
Foam samples were taken at preset time intervals as 2, 4, 8 and 16 minutes. The froth
products from various time increments were analyzed by atomic absorption
spectrometry (AAS) to determine the amount of metal ions that floated. After the
experiments the flotation cell was cleaned using 1M HNO3, with double distilled water.

24
Table 3.3. Experimental Conditions for the Ion Flotation Tests

Machine Type Denver Equipment Co.

Volume 1 liter
Rotor Speed 750 rpm
Air Flow Rate 50 ml/min.
Sodium Dodecyl Sulfate or
Collector Hexadecyl trimethyl
ammoniumbromide
Frother Ethanol or MIBC
pH From 4 to 12
Froth Removal Times 2, 4, 8 and 16 minutes

Froth
Air

Flotation cell

Frother (Ethanol or MIBC)

+
Collector
+
Heavy metal ions
(Cu, Zn, Cr, Ag)

Figure 3.1. A schematic view of the Flotation Machine

25
3.2.2. Atomic Absorption Spectrometry (AAS)

Atomic Absorption Spectrometry (AAS) uses the absorption of radiation by free

gaseous atoms in order to achieve quantitative determination of elements (Welz and
Sperling, 1998). An atomic absorption spectrometer measures the absorbance which is
the logarithm of the rate of incident light power (Po) to transmitted light power (P) :

A = Log Po / P (3.1)
There is a relationship between Po and P when a light beam is decreased by the
medium through which it passes:
P = Poexp(-kL) (3.2)

Where k : absorption coefficient which is a function of wavelength of light, number of

atoms in the ground state per unit volume.
L : path length in medium
There are two main components in an atomic absorption spectrometer: atom cell
which creates atoms at the free gaseous ground state, and optical system to measure the
signal. Atom cell dissolvates the liquid sample and dissociates analyte elements into
their free gaseous ground state form in which the atoms are available to absorb radiation
coming from light source and to create a measurable signal which is proportional to
concentration (Tyson and Haswell 1991). The atomizer, in which the analyte is
atomized, is flame, graphite tube or quartz tube. In flame atomization fixed aliquot of
measurement solution is converted into an aerosol in nebulizer and transported into the
flame which must have enough energy both vaporize and atomize the sample (Welz and
Sperling 1998).

3.2.3. Surface Tension Measurements

The surface tension of SDS solutions were measured at 25 oC with a Krüss K10
ST model using the ring type surface tension method. All glassware for the
measurements was throughly cleaned using concentrated nitric acid solution and rinsed
with double distilled water. Between measurements, the ring was rinsed many times in
double distilled water and then burned in a flame. Different concentrations of SDS
solutions from 10-2 M to 10-6 M were prepared. Then a fixed amount of sample (35 ml)
was taken for the measurement in each case. Before the sample was taken it was mixed
26
for 1 minute and all samples were made to wait for 2 minutes to obtain stability. Each
surface tension value presented here was the averaged value of three measurements.

27
 CHAPTER 4

RESULTS AND DISCUSSION

4.1. Surfactants

The role of surfactant molecules in ion flotation is significant which was

discussed in Chapter II. The forms of surfactant molecules in aqueous system change
with their concentrations. In order to study these changes surface tension measurements
were done as a function of SDS concentration and the results were discussed in the
following paragraphs.

Surface Tension

The surface tensions of the aqeous SDS solutions were measured and the results
were presented in Figure 4.1 as surface tension (γ) versus concentration (Conc.) curves.
It is seen that there are three regions and two breaks in the curve. The second break at
around 8x10 –3 mol/ L is so distinct that the surface tension values level off and show a
nearly constant value after this concentration (Region III). This is the critical micelle
concentration (CMC) which is the concentration at which the single molecules come
together to form aggregates known as micelles. In region I and II where the
concentrations less than CMC, however surfactant molecules are in their single form
and contributes to the decrease in surface tension. In region II, however, the slope of
the curve is constant, meaning that the surface has reached a monolayer coverage.
Surface tension, however continues to decrease due to exchange between the bulk
molecules and the surface molecules constantly and increase in the rate of this process
with an increase in concentration.

28
 80
Sodium Dodecyl Sulfate
Region I at 25oC

Surface Tension (dyn/cm) 70

Air
Water
60
Region II
A
50 -10 2 W
Γs = 6,58.10 mol/cm
s o2
a = 25,3 A CMC
40

Region III

30

0.0001 0.001 0.01 0.1

SDS Concentration, (M)

Figure 4.1. Surface Tension of SDS solution at 25 oC

The slope of this curve could be used to calculate the adsorption of surfactant
molecules at air/water interface using Gibb’s adsorption equation. The most general
form of Gibbs adsorption equation,
dγ = -∑ Γ dµ (4.1)
where dγ : the change in surface tension of the solvent,
Γ : the surface excess concentration of any component of the system,
dµ : the change in chemical potential of any component of the system,
is fundamental to all adsorption processes (Rosen 1989).
–2
For dilute solutions (10 M or less) which contain only one nondissociating
surface active solute, the activity of the solvent and the activity coefficient of the solute
can be considered to be constant. Thus,
dγ = - RT Γ dlnC (4.2)
dγ = -2.303 RT Γ dlogC (4.3)
which is the formula in which the Gibbs equation is commonly used for solutions of
surfactants.

29
 When γ is in mN/m ( equal to mJ/m2 ) and R = 8.31 J/mol K, then Γ is in
mol/1000m2. From the surface excess concentration, the area per molecule at the
interface as, in square angstroms (Ao2) is calculated from the relation.

as = 10 16/ N Γ (4.4)

where N : Avogadro’s number and Γ is in mol/cm2.

The surface excess concentration ( Γ ) was calculated by using equation (4.3)
–10
and found 6.58.10 mol/cm2. Applying this value in equation (4.4) the area per
molecule at the interface (as) was obtained as 25.3 Ao2 per SDS molecule. This value
could be helpfull to imagine in comparing the sizes of the surfactant heads and the ions.

4.2. Frothers

Frothers in ion flotation play very important role due to their effect on bubble
formation. They adsorp at air/water interface and influence surface tension. This effect
was studied and the results were presented in Figure 4.2. It is seen that the effect of a
frother on surface tension changes as a function of its concentration and the presence of
other species (such as surfactants and metal ions) in the system. And also seen that in
the case of increasing concentrations of MIBC, surface tension decreased sharply
compared to increasing ethanol concentrations. This might be due to the number of
carbon atoms that found in the structure of MIBC and ethanol (MIBC has six, ethanol
has two carbon atoms in their structure).
The effect of ethanol on surface tension was small when also a surfactant is
present in the system. This might be due to the availibility of ethanol for surface to
decrease surface tension. That is it is not available for surface when surfactant
molecules are present. However, the presence of metal ions decreased their influence on
the ethanol action. Figure 4.4 gives these results for different metal ions. The varying
effects of metals on the action of ethanol to decrease surface tension shows the varying
affinities of metal ions on surfactant molecules. If a metal ion has more affinity to
surfactant, it will attach to it and decrease its effect on the action of ethanol. Ethanol
will be free to adsorp at interface and decrease surface tension at the concentrations
used in this study (Figure 4.3.).

30
 80

70

Surface Tension (dyn/cm)

60

50

10-4 M SDS, Ethanol

40
5.10-4 M SDS, Ethanol
Ethanol
MIBC
30 10-4 M SDS, MIBC
5.10-4 M SDS, MIBC

0,01 0,1 1

Ethanol / MIBC Concentration, (%)

Figure 4.2. Surface Tension of Ethanol / MIBC and SDS Solution.

80

70
Surface Tension (dyn/cm)

60

50

40 Ethanol
5.10-4 M SDS, Ethanol
-4
5.10 M SDS, Ethanol, Cr: 10ppm
30 5.10-4 M SDS, Ethanol, Zn: 10ppm
5.10-4 M SDS, Ethanol, Cu: 10ppm

20
0,1 1

Ethanol Concentration, (%)

Figure 4.3. Surface Tension of Ethanol / MIBC and SDS Solution with Metals.

31
 80 80

70

Surface Tension (dyn/cm)

Surface Tension (dyn/cm)

70
60

60 50

SDS SDS
10-4 M SDS, Ethanol 40 10-4 M SDS, Ethanol
5.10-4 M SDS, Ethanol 5.10-4 M SDS, Ethanol
50 10-4 M SDS, Ethanol, Cu : 10ppm
-4
10 M SDS, Ethanol, Zn: 10ppm
-4
5.10-4 M SDS, Ethanol, Cu : 10ppm 30 5.10 M SDS, Ethanol, Zn : 10ppm
-4
10-4 M SDS, Ethanol, Cu : 50ppm 10 M SDS, Ethanol, Zn : 50ppm
-4
5.10 -4 M SDS, Ethanol, Cu : 50ppm 5.10 M SDS, Ethanol, Zn : 50ppm

40 20
0,1 1 0,1 1

Ethanol Concentration, (%) Ethanol Concentration, (%)

70 80

65
Surface Tension (dyn/cm)
Surface Tension (dyn/cm)

60
60

55
40
SDS
-4
10 M SDS, MIBC, Ag: 10ppm 10-4 M SDS, Ethanol
50
5.10-4 M SDS, MIBC, Ag: 10ppm 5.10-4 M SDS, Ethanol
10-4 M SDS, MIBC, Ag: 100ppm 10-4 M SDS, Ethanol, Cr: 10ppm
5.10-4 M SDS, MIBC, Ag: 100ppm 5.10-4 M SDS, Ethanol, Cr: 10ppm
45 MIBC 20
10-4 M SDS, Ethanol, Cr: 50ppm
10-4 M SDS ,MIBC
-4 5.10 -4 M SDS, Ethanol, Cr: 50ppm
5.10 M SDS, MIBC

40 0,1 1
0,1 1
MIBC Concentration, (%) Ethanol Concentration, (%)

Figure 4.4. The Effect of Ethanol / MIBC Solution and Their Mixture of SDS with /
without Different Concentrations of Metals on Surface tension.

32
4.3. Metals

4.3.1. Forms of Metal Ions in Water as a Function of pH

pH is a significant factor for determining the form of the metallic species.

Because pH of the solution influences the distribution of the various species. When
determining various metal species equilibrium models for many metals are constructed
using the set of equations used for simple acid-base calculations. First, total
concentrations of all components are stated; then all possible species are identified; and
mass balances, a charge balance and equilibrium equations are written. However, it is
time wasting to solve these equations manually. Because of this, computer solution was
needed. Instead of this way, Visual Minteq ver.2.15 was used. After obtaining the form
of the metallic species, graphs were drawn for copper, zinc, silver and chromium
concentrations as a function of pH and given in Figures 4.5, 4.6, 4.7, 4.8.
The pH is one of the principal factors influencing the separation of ions by flotation, as
it determines the magnitude and sign of the charge on ions. This makes one to decide
which surfactant to use in flotation.
Figure 4.5 gives the distribution of copper species as a function of pH for 10ppm
concentration. It is seen that there are negatively and positively charged Cu species
between pH: 4 and 12. For pH values between 4 and 11, copper and its species are
positively charged, however, for pH values higher than 11 they are negatively charged.
As a result, knowing the type of species present in the solution will help one to decide
the most suitable surfactant, anionic or cationic, to use.
Figure 4.6 gives the distribution of zinc species as a function of pH for 10ppm
concentration. In case of low pH values (<pH 5), posively charged zinc (II) species are
dominant. In case of high pH values (pH 5-12), however, there are several zinc species
with different charges.

33
 Cu 2+ Cu(OH)3-
1,4e-4

1,2e-4
Concentration, mg/L
1,0e-4

8,0e-5 Cu(OH)2

6,0e-5
2+
Cu3(OH)4
4,0e-5

2,0e-5 2+ CuOH+ 2-
Cu2(OH)2 Cu(OH)4

0,0
2 4 6 8 10 12

pH
Figure 4.5. Forms of Copper (10 mg/L) in Water as a Function of pH

1,4e-4 Zn 2 +
Zn(OH)- 3
1,2e-4
Concentration, mg/L

Zn(OH)2
1,0e-4

8,0e-5

6,0e-5 Zn(OH)4 2-

4,0e-5

2,0e-5 ZnOH +

0,0
2 4 6 8 10 12

pH
Figure 4.6. Forms of Zinc (10 mg/L) in Water as a Function of pH

34
 Figure 4.7 gives the distribution of silver species as a function of pH for 10mg/L
concentration. According to this Figure, there are negatively charged silver species for
pH values from 10 to 12. At low pH values, positively charged silver species are
dominant.
Figure 4.8 gives the distribution of chromium species as a function of pH for
10mg/L concentration. In low values, the main aqeous Cr (III) species are Cr3+,
Cr(OH)2+, Cr(OH)3 , Cr(OH)-4 and Cr(OH)3+. Cr3+ species are seen only at a pH values
lower than 4. When the pH value is higher than 10, the species with negative charge
becomes dominant.

1e-4
Ag+

8e-5
Concentration, mg/L

6e-5

4e-5

AgOH
2e-5

Ag(OH)2-
0
2 4 6 8 10 12

pH

Figure 4.7. Forms of Silver (10 mg/L) in Water as a Function of pH

35
 1,2e-4
Cr3+
Cr(OH) 2+ Cr(OH)3
1,0e-4

Concentration, mg/L
8,0e-5

CrO2-
6,0e-5

4,0e-5

Cr(OH)2+
2,0e-5
Cr(OH)-4
0,0
2 4 6 8 10 12

pH
Figure 4.8. Forms of Chromium (10 mg/L) in Water as a Function of pH

Forms of metal ions in water in case of higher concentrations as a function of pH

were represented in Appendix B. Increasing total copper, zinc, silver and chromium
concentrations influence the metal species, their concentrations in water and their sign
of the charge at the given pH value.

4.4. Ion Flotation Studies

Flotation experiments were carried out as a function of time (2, 4, 8, 16 minutes)

and metal (Cu, Zn, Ag, Cr) recoveries were calculated using the procedure given in
Chapter III. Sodium dodecyl sulfate / hexadecyl trimethyl ammoniumbromide and
ethanol/ methylisobutyl carbinol were used as collectors and frothers respectively. 50
ml/min was selected as a flowrate. The results were presented in following paragraphs
for each metal ion.

36
4.4.1. Copper

The results of copper were presented in Figues 4.9 and 4.10 for different ethanol
concentrations as 0.1%, 0.5% and 1% for each surfactant concentration of 10-4 M,
–4
5x10 M and 10-3 M. These results were also presented as a tridimentional plot in
Figure 4.11 to look at the picture differently. SDS was used as an anionic surfactant at
the pH used (pH 4) due to positive charge of the ionic species present (see also Figure
4.5). At 10-4 M of SDS, the copper recovery was very low. The change in ethanol
concentration did not make any difference in this result. At 5x10-4 M SDS, the copper
recoveries were 59%, 74% and 51% for 0.1, 0.5, and 1.0% of ethanol concentrations
respectively. At 10-3 M SDS, the copper recoveries were 44%, 70%, 52% for 0.1, 0.5,
and 1.0% of ethanol concentrations, respectively. As it is seen from Figure 4.11 that at
low concentrations of surfactant changing ethanol concentration did not make any
difference where there is no collector metal ion attachment. At higher concentrations,
however, the recoveries changed with ethanol concentration and an optimum was
observed around 0.5%.
When ethanol concentrations were 0.1% and 1%, the production of foam was
affected and stopped after 16 minutes. However, it continued up to 32 minutes in case
of 0.5% case. This results was explained by Duyvesteyn (1994) as follows. According
to these investigators, at low concentrations of alcohol, the metal-collector complex
may be stabilized by alcohol molecules through “ hydrophobic interaction ” with the
hydrocarbons chains of the frother. The detrimental action of higher concentrations of
alcohol may be due to fact that the metal- collector complexes are stabilized so well in
the aqeous solution that they are less likely to adsorb at the air-interface. Also at the
higher alcohol 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.

37
 100
pH :4 5.10-4M SDS
Airflow rate: 50ml/min
80

Cu Recovery,%
60 0,1% Ethanol
0,5% Ethanol
1% Ethanol

40

20

0 5 10 15 20 25 30

Time,min.

Figure 4.9. Effect of Ethanol Concentration on Copper Recovery as a Function of Time.

(Initial copper concentration: 10 mg/L; SDS concentration : 5.10-4 M; pH: 4;
Airflow rate: 50ml/min.)

100

pH :4 10-3M SDS
Airflow rate: 50ml/min
80

0,5% Ethanol
Cu Recovery,%

60
1% Ethanol

40 0,1% Ethanol

20

0 2 4 6 8 10 12 14 16

Time,min.

Figure 4.10. Effect of Ethanol Concentration on Copper Recovery as a Function of

Time. (Initial copper concentration: 10 mg/L; SDS concentration : 10-3 M;
pH: 4; Airflow rate: 50ml/min.)

38
 Different air flowrate values of 50, 150, 250 ml/min were also tested for 5.10-4
M SDS, pH: 4 and 0.5% of ethanol condition. It is seen from the Figure 4.12 that 250
ml/min. gave the maximum recovery but the amount of foam produced was so high.

1,0
Airflow rate: 50ml/min
pH =4, Cu

0
10
0,8
20
30
Ethanol Concentration,%

40
50
60
0,6 70

0,4

0,2

0,0002 0,0004 0,0006 0,0008 0,0010

Surfactant Concentration,M

Figure 4.11. Effect of Ethanol Concentration and Surfactant Concentration on Copper

Recovery as a Function of Time. (Initial copper concentration: 10 mg/L;
Airflow rate : 50 ml/min.; pH: 4)

39
 100
pH :4
5.10-4 M SDS
250ml/min 0,5% Ethanol
80

Cu Recovery,% 60 50ml/min

150ml/min
40

20

0 5 10 15 20 25 30

Time,min.

Figure 4.12. Effect of Airflow rate on Copper Recovery as a Function of Time. (Initial
copper concentration: 10 mg/L; SDS concentration : 5.10-4 M; pH: 4;
Ethanol: 0.5%.)

The copper recoveries were also plotted as a function of the water recoveries and
presented in Figures 4.13 and 4.14. This kind of analyzing has not coincided in
literature yet. These type of plotting helps one to have also an idea about the amount of
water collected during separation. Scorzelli and Fragomeni et. al, 1999, discussed in the
large volume of foam but their results did not show the recovery exactly. Scorzelli et al.
1999, Lazaridis et al. 2004, Matis et al. 2005, Girek et al. 2004, Kozlowski et al. 2002,
Charewicz et al. 1999, determined the recovery of metals as a function of time but did
mention water recovery.
In Figure 4.13, the crossed line which is from one corner to another is 50 – 50
split line. This means no separation occurs at that condition. If the flotation results
approach to the axis of y, it means metal concentration is in the froth phase but if the
results approach to the axis of x, it is understand that metal concentration is in the
flotation cell. The analyzing the results this way also showed that the highest recovery
was at 0.5% ethanol and 5.10–4 M SDS concentrations at pH 4.

40
 80

60
Cu Recovery, %

40 0.1% Ethanol
0.5% Ethanol
1% Ethanol

20
Cu : 10 ppm, SDS : 5.10-4M
pH = 4 Airflow rate : 50ml/min.

0 20 40 60 80

Water Recovery, %

Figure 4.13. Copper Recovery as a Function of Water Recovery. (Initial copper

concentration: 10 mg/L; Airflow rate: 50 ml/min.; pH: 4, SDS: 5.10 –4M)

When the initial copper concentration was increased to 50 mg/L in the presence
of 5.10–4 M SDS and 0.5 % ethanol at pH 4 , the recovery decreased to 42%. This might
be due to the higher number of copper ions compared to the surfactant molecules
present. The number of copper ions is equal to 9.48x1019 and 47.25x1020 in case of 10
mg/L and 50 mg/L respectively. The number of surfactant molecules, on the other hand
did not changed and stayed as 30.1x1019 which may not be enough for 50 mg/L copper
concentration. This also supports the mechanism proposed for ion flotation discussed in
Chapter II. That is metal ions attach to surfactant molecules with opposite charge on
them and therefore attach to the air bubble and floats (see also Figure 2.2a and b).

41
 80

60
Cu Recovery, %

40 0.1% Ethanol
0.5% Ethanol
1% Ethanol

20
Cu : 10 ppm, SDS : 10-3M
pH = 4 Airflow rate : 50ml/min.

0 20 40 60 80

Water Recovery, %

Figure 4.14. Copper Recovery as a Function of Water Recovery. (Initial copper

concentration: 10 mg/L; Airflow rate : 50 ml/min.; pH: 4, SDS : 10 –3 M)

50

40
Cu Recovery, %

30 Cu : 50 ppm, SDS : 5.10-4M

0.5 % Ethanol, pH = 4
Airflow rate : 50ml/min.
20

10

0 10 20 30 40 50

Water Recovery, %

Figure 4.15. Copper Recovery as a Function of Water Recovery. (Initial copper

concentration: 50 mg/L; Airflow rate: 50 ml/min.; pH: 4, SDS: 5.10 –4M)

42
4.4.2. Zinc

The results of zinc were presented in Figues 4.17 and 4.18 for different ethanol
concentrations as 0.1%, 0.5% and 1% for each surfactant concentration of 10-4 M,
5.10–4 M and 10-3 M. These results were also presented as a tridimentional plot in
Figure 4.16 to see the picture clearly. SDS was used as an anionic surfactant at the pH
value of 4 due to charge of the ionic species present (in Figure 4.6). The zinc recovery,
at 10-4 M of SDS, was so low. At 5x10-4 M SDS, the zinc recoveries for 0.1, 0.5, and
1.0% of ethanol concentrations were 69%, 62% and 58% respectively. At 10-3 M SDS,
the zinc recoveries for 0.1, 0.5, and 1.0% of ethanol concentrations were 67%, 63%,
55%, respectively. As it is seen from Figure 4.16 that at higher concentrations of
surfactant, the recoveries changed with ethanol concentration and an optimum was
observed around 0.1%.

1,0
pH = 4, Zn
Air flow rate: 50ml/min.

0
0,8 10
20
30
Ethanol Concentration, %

40
50
60
0,6

0,4

0,2

0,0002 0,0004 0,0006 0,0008 0,0010

Surfactant Concentration, M

Figure 4.16. Effect of Ethanol Concentration and Surfactant Concentration on Zinc

Recovery as a Function of Time. (Initial zinc concentration: 10 mg/L; pH:
4)

43
 The recoveries of zinc were also drawn as a function of the water recoveries and
presented in Figures 4.17 and 4.18. The results also showed that the highest recovery
(69%) was at 0.1% ethanol and 5.10–4 M SDS concentrations at pH 4.

80

60
Zn Recovery, %

40 0.1% Ethanol
0.5% Ethanol
1% Ethanol

20
Zn : 10 ppm, SDS : 5.10-4M
pH = 4 Airflow rate : 50ml/min.

0 20 40 60 80

Water Recovery, %

Figure 4.17. Zinc Recovery as a Function of Water Recovery. (Initial Zinc

concentration: 10 mg/L; Airflow rate: 50 ml/min.; pH: 4, SDS: 5.10 –4M)

In Figure 4.19, the initial zinc concentration was increased to 50 ppm in the
presence of 5.10–4 M SDS and 0.1 % ethanol at pH 4 , the recovery decreased to 41%. It
might be because of the high number of zinc ions compared to the surfactant molecules
present. The number of zinc ions is equal to 9.21x1019 and 4.60x1020 in case of 10 mg/L
and 50 mg/L respectively. The number of surfactant molecules, on the other hand did
not changed and stayed as 30.1x1019 which is not enough for 50 mg/L zinc
concentration.

44
 70

60

Zn Recovery, % 50

40
0.1% Ethanol
30 0.5% Ethanol
1% Ethanol

20

Zn : 10 ppm, SDS : 10-3M

10 pH = 4 Airflow rate : 50ml/min.

0 20 40 60 80

Water Recovery, %

Figure 4.18. Zinc Recovery as a Function of Water Recovery. (Initial Zinc

concentration: 10 mg/L; Airflow rate : 50 ml/min.; pH: 4, SDS : 10 –3 M)

50

40
Zn Recovery, %

30

20

10 SDS : 5.10-4M, 0.1% Ethanol

pH = 4, C Zinc =50ppm
Air Flowrate : 50ml/min.
0
0 10 20 30 40 50

Water Recovery, %

Figure 4.19. Zinc Recovery as a Function of Water Recovery. (Initial zinc

concentration: 50 mg/L; Airflow rate: 50 ml/min.; pH: 4, SDS: 5.10 –4M)

45
4.4.3. Silver

In the flotation studies of silver, firstly , ethanol was used as a frother, but the
presence of different ethanol concentrations did not influence the silver recovery
appareantly in the whole pH range. Because of this case, another type of frother as
known as methly isobutly carbinol (MIBC) was used in the experiments of silver. For
the selected MIBC concentrations, 0.01%, 0.05% and 0.1% for each surfactant
concentration of 10-4 M, 5.10 –4
M and 10-3 M were performed and presented in Figure
4.20 as a tridimensional plot. At 10-4 M SDS, the silver recoveries for 0.01, 0.05, and
0.1% of MlBC concentrations were 50%, 47% and 73% respectively. At 5x10-4 M SDS,
the silver recoveries for 0.01, 0.05, and 0.1% of MIBC concentrations were 49%, 53%,
45%, and at 10-3 M SDS, recoveries of silver were 47%, 50% and 39% respectively.
These results are seen in Figures 4.21, 4.22 and 4.23 clearly. As it is seen from Figure
4.20 that at higher concentrations of surfactant, the recoveries did not change with
MIBC concentration and an optimum was observed around 0.1%.
For the tests using a higher concentration of collector (10–3 M), a greater amount
of foam was formed, causing the decrease in the removal of silver flotation. According
to Pinfold (1972), the decrease of the species removal for increasing collector
concentrations can be due to competition between coligend-collector complex and free
ion collectors for a place in the surface of the bubble.
In Figure 4.24, silver concentration was increased to 100 ppm in the presence of
10–4 M SDS and 0.1 % MIBC at pH 4 , the recovery decreased to 41%. It might be
because of the high number of silver ions compared to the surfactant molecules present.
The number of silver ions is equal to 5.58x1019 and 5.58x1020 in case of 10 mg/L and
100 mg/L respectively. The number of surfactant molecules, on the other hand did not
changed and stayed as 30.1x1019 which is not enough for 100 mg/L silver concentration.

46
 0,10
Airflow rate: 50ml/min
pH =4, Ag

40
0,08 45
50
55
MIBC Concentration,%

60
65
70
0,06
75

0,04

0,02

0,0002 0,0004 0,0006 0,0008 0,0010

Surfactant Concentration,M

Figure 4.20. Effect of MIBC Concentration and Surfactant Concentration on Silver

Recovery as a Function of Time. (Initial silver concentration: 10 mg/L;
Airflow rate : 50 ml/min.; pH: 4)

47
 80

60
Ag Recovery, %

40 0.01% MIBC
0.05% MIBC
0.1% MIBC

20
Ag : 10 ppm, SDS : 10-4M
pH = 4 Airflow rate : 50ml/min.

0 20 40 60 80

Water Recovery, %

Figure 4.21. Silver Recovery as a Function of Water Recovery. (Initial Silver

Concentration: 10 mg/L; Airflow rate: 50 ml/min.; pH: 4, SDS: 10 –4 M )

60

50
Ag Recovery, %

40

30 0.01% MIBC
0.05% MIBC
0.1% MIBC
20

Ag : 10 ppm, SDS : 5.10-4M

10 pH = 4 Airflow rate : 50ml/min.

0 10 20 30 40 50 60

Water Recovery, %

Figure 4.22. Silver Recovery as a Function of Water Recovery. (Initial Silver

Concentration: 10 mg/L, pH: 4, SDS: 5.10 –4M)

48
 60

50

Ag Recovery, %
40

30 0.01% MIBC
0.05% MIBC
0.1% MIBC
20

Ag : 10 ppm, SDS : 10-3M

10 pH = 4 Airflow rate : 50ml/min.

0 10 20 30 40 50 60

Water Recovery, %

Figure 4.23. Silver Recovery as a Function of Water Recovery. (Initial Silver

Concentration: 10 mg/L; Airflow rate: 50 ml/min.; pH: 4, SDS: 10 –3 M )

50

40
Ag Recovery, %

30

20

10 SDS :10-4M, 0.1% MIBC

pH = 4, C Silver =100ppm
Air Flowrate : 50ml/min.
0
0 10 20 30 40 50

Water Recovery, %

Figure 4.24. Silver Recovery as a Function of Water Recovery. (Initial silver

concentration: 100 mg/L; pH: 4, SDS : 10 –4 M)

49
4.4.4. Chromium

The results given in Figures 4.25 and 4.26 show the effect of different ethanol
concentrations as 0.1%, 0.5% and 1% and SDS concentration of 10-4 M, 5.10 –4
M and
10-3 M on flotability of chromium (III). The recoveries of chromium, at 10-4 M of SDS,
were low. The chromium recoveries for 0.1, 0.5, and 1.0% of ethanol concentrations at
5x10-4 M SDS, were 40%, 40% and 46% respectively. At 10-3 M SDS, the chromium
recoveries for 0.1, 0.5, and 1.0% of ethanol concentrations were 49%, 50%, 48%,
respectively. This is seen from Figure 4.27 as the tridimentional plot obviously. As it is
seen from the figure that at higher concentrations of surfactant and ethanol, the
recoveries did not change and low values were observed for all the ethanol
concentrations.

50

40
Cr Recovery, %

30

0.1% Ethanol
0.5% Ethanol
20 1% Ethanol

10 Cr : 10 ppm, SDS : 5.10-4M

pH = 4 Airflow rate : 50ml/min.

0 10 20 30 40 50

Water Recovery, %

Figure 4.25. Chromium Recovery as a Function of Water Recovery. (Initial Chromium

Concentration: 10 mg/L; pH: 4, SDS : 5.10 –4 M )

50
 50

40
Cr Recovery, %

30

0.1% Ethanol
0.5% Ethanol
20 1% Ethanol

10 Cr : 10 ppm, SDS : 10-3M

pH = 4 Airflow rate : 50ml/min.

0 10 20 30 40 50

Water Recovery, %
Figure 4.26. Chromium Recovery as a Function of Water Recovery. (Initial Chromium
Concentration: 10 mg/L; pH: 4, SDS : 10 –3 M )

1,0
Airflow rate: 50ml/min
pH =4, Cr 3+

0,8 0
10
20
Ethanol Concentration,%

30
40
50
0,6 60
70

0,4

0,2

0,0002 0,0004 0,0006 0,0008 0,0010

Surfactant Concentration,M

Figure 4.27. Effect of Ethanol and Surfactant Concentrations on Chromium Recovery as

a Function of Time. (Initial chromium concentration: 10 mg/L; pH: 4)

51
4.5. Effect of Water Chemistry

4.5.1. pH of the solution

4.5.1.1. Copper

The effect of solution pH on ion flotation was also tested since there is a
distribution of ionic species for varies pH values (see Figure 4.5). The results of these
experiments were presented in Figure 4.28 for copper. The sign of the charge of copper
ion was positive at pH values of 6, 8 and 10 and therefore anionic surfactant, SDS, was
used. The highest recovery was obtained in the presence of 5.10–4 M of SDS at pH 10
(90%). The recoveries were 66% and 35% for pH 6 and 8, respectively. On the other
hand, since the sign of the species present at pH 12 was negative, a cationic surfactant,
HTAB, was used. The results of the experiments were obtained in the presence of 5.10-4
M of HTAB at pH values of 10 and 12 were also given at Figure 4.28. The recoveries
obtained were 48% and 79% for pH 10 and 12, respectively. It is observed from the
figure that anionic surfactant, SDS, had no influence on the copper recovery at pH value
of 12 compared to cationic surfactant, HTAB.

100

80
Cu Recovery, %

60
pH = 6
pH = 8
40 pH = 10
pH = 12 with HTAB
pH = 10 with HTAB

20 Cu : 10 ppm, SDS / HTAB: 5.10-4M

Airflow rate : 50ml/min.
0.5% Ethanol

0 20 40 60 80 100

Water Recovery, %
Figure 4.28. Copper Recovery as a Function of pH. (Initial copper concentration: 10
mg/L)

52
4.5.1.2. Zinc

The effect of solution pH on zinc flotation was tested since there is a distribution
of ionic species for varies pH values (see Figure 4.6). Figure 4.29 shows the recovery of
zinc as a function of pH. The sign of the charge of zinc ion was positive at pH values of
6, 8 and 10 and therefore anionic surfactant, SDS, was used. There was no flotation at
pH 10. However, the recoveries of 68% and 71% were obtained in the case of pH 6 and
8, respectively. The dominant species were negatively charged at pH of 12 and therefore
a cationic surfactant, HTAB was used and the recoveries of zinc at pH of 10 and 12
were obtained as 46% and 72%, respectively. As it is seen in Figure 4.29, there was no
recovery at pH of 10 in the presence of SDS compared to HTAB because of using low
ethanol concentration (0.1%).

80

60
Zn Recovery, %

40
pH = 6
pH = 8
pH = 10 with HTAB
pH = 12 with HTAB
20
Zn:10ppm, SDS / HTAB: 5.10-4M
Airflow rate:50ml/min
0.1 % Ethanol

0 20 40 60 80

Water Recovery, %

Figure 4.29. Zinc Recovery as a Function of pH. (Initial Zinc Concentration: 10 mg/L)

53
4.5.1.3. Silver

The effect of pH of solution on silver recovery was tested since there is a

distribution of ionic species for varies pH values (see Figure 4.7) and presented in
Figure 4.30. As it is seen in Figure 4.7, at pH values of 6, 8, 10 silver is positively
charged and therefore anionic surfactant, SDS, was used. The recoveries of 25% 73%
and 72% and were obtained in the case of pH 6, 8 and 10 respectively. The best
recovery of silver is 10–4 M SDS, 0.1% MIBC and pH value of 4. The dominant species
were negatively charged at pH of 12 and therefore a cationic surfactant, HTAB were
used and the recoveries of silver at pH of 10 and 12 were obtained as 47% and 71%,
respectively. Figure 4.30 showed that HTAB was not effective at pH of 10 compared to
SDS.

80

60
Ag Recovery, %

40 pH = 6
pH = 8
pH = 10
pH = 12 with HTAB
pH = 10 with HTAB
20
Ag : 10 ppm, SDS / HTAB : 10-4M
pH = 4 Airflow rate : 50ml/min.
Ethanol : 0.1%

0 20 40 60 80

Water Recovery, %

Figure 4.30. Silver Recovery as a Function of pH. (Initial Silver Concentration: 10

mg/L)

54
4.5.1.4. Chromium

The effect of solution pH on chromium recovery was tested since there is a

distribution of ionic species for varies pH values (see Figure 4.8) and presented in
Figure 4.31. According to Torem, 2001, the highest chromium removal occurs in the pH
range 4 – 6. As it is seen in Figure 4.8, at pH values of 6, 8, 10 chromium is positively
charged and therefore anionic surfactant, SDS, was used. The recoveries of 36% , 97%
and 29% were obtained in the case of pH 6, 8 and 10 respectively. However, in Figure
4.27, at pH value of 4 the recovery of chromium was around 50% for the same
condition (10–4 M SDS, 0.1% MIBC). The dominant species were negatively charged at
pH of 12 and therefore a cationic surfactant, HTAB were used and the recoveries of
chromium at pH of 10 and 12 were obtained as 48% and 86%, respectively.

100

80
Cr Recovery, %

60

pH = 6
pH = 8
40
pH = 10
pH = 12 with HTAB
pH = 10 with HTAB
20
Cr:10ppm, SDS: 5.10-4M
Airflow rate:50ml/min
0.5 % Ethanol
0 20 40 60 80 100

Water Recovery, %

Figure 4.31. Chromium Recovery as a Function of pH. ( Initial Chromium

Concentration: 10 mg/L )

55
4.5.2. Ionic Strength

In this part of the study, the effect of ionic strength was studied. For this purpose
a tap water with Na+, Mg2+, Ca2+ ions were used. The average concentrations of those
elements are given in Table 4.1:

Table 4.1. Concentrations of Na, Ca, Mg in Tap Water Used in Studies.

Element Na Ca Mg
Concentration
18 200 26
(mg/L)

The results of this study were given in Figures 4.32, 4.33, 4.34 and 4.35. These
experiments were done at different concentrations as 10, 50 mg/L (for copper, zinc and
chromium) and 100 mg/L (for silver).
As it is seen from the Figure 4.32, the copper recoveries decreased from 89.5%
to 43% and from 88% to 44% in the case of tap water for 10 and 50 mg/L
concentrations respectively. In Figure 4.33, zinc recoveries decreased for 10 and 50
mg/L, from 69% to 39% and from 41% to 42%, respectively. The recovery of
chromium gave the similar reduction as seen in Figure 4.35. The recoveries reduced
from 97% to 95% for 10 mg/L and from 90% to 82% for 50 mg/L concentrations. In
Figure 4.34, results for silver recoveries decreased from 73% to 51% and from 41% to
40% for 10 and 100 mg/L respectively.
This drastic decrease can be explained by the presence of excess Na, Mg, Ca
ions that compete with copper. So the metal ions can not find enough dodecyl sulfate
molecules to attach to. Analysis of these ions (Ca, Mg and Na) were also conducted in
the froth samples to prove this. It was found out that 98% of the ions present in the cell
was floated.
In Figure 4.35, chromium concentration was increased to 50 mg/L in the
presence of 5.10–4 M SDS and 0.5 % ethanol at pH 8 , the recovery decreased to 81%. It
might be because of the high number of chromium ions compared to the surfactant
molecules. The number of chromium ions is equal to 11.6x1019 and 58x1019 in case of
10 mg/L and 50 mg/L respectively. The number of surfactant molecules, on the other

56
hand did not changed and stayed as 30.1x1019 which is not enough for 50 mg/L
chromium concentration.

100

80
Cu Recovery, %

60

SDS : 5.10-4M
0.5 % Ethanol, pH = 4
40 Airflow rate : 50ml/min.

Cu : 10ppm
20 Cu : 50ppm
Cu : 10ppm in tap water
Cu : 50ppm İn tap water

0
20 40 60 80 100

Water Recovery, %
Figure 4.32. Effect of Ionic Strength on Copper Recovery. (SDS: 5.10–4 M, 0.5%
Ethanol, pH: 4, Airflow rate : 50 mL/min.)

80

60
Zn Recovery, %

40 SDS : 5.10-4M
0.1 % Ethanol, pH = 4
Airflow rate : 50ml/min.

20 Zn : 10ppm
Zn : 50ppm
Zn : 10ppm in tap water
Zn : 50ppm İn tap water

0
20 40 60 80

Water Recovery, %
Figure 4.33. Effect of Ionic Strength on Zinc Recovery. (SDS : 5.10–4 M, 0.1% Ethanol,

57
 pH : 4,)
80

60
Ag Recovery, %

40
SDS : 10-4M
0.1 % MIBC, pH = 4
Airflow rate : 50ml/min.

20 Ag: 100ppm in tap water

Ag : 10ppm in tap water
Ag: 10ppm
Ag : 100ppm

0
20 40 60 80

Water Recovery, %

Figure 4.34. Effect of Ionic Strength on Silver Recovery. (SDS : 10–4 M, 0.1% MIBC,
pH : 4, Airflow rate : 50 mL/min.)

100

80
Cr Recovery, %

60

SDS : 5.10-4M
40 0.5 % Ethanol, pH = 8
Airflow rate : 50ml/min.

Cr: 50ppm
20 Cr : 10ppm in tap water
Cr: 50ppm in tap water
Cr : 10ppm

0
20 40 60 80 100

Water Recovery, %

58
Figure 4.35. Effect of Ionic Strength on Chromium Recovery. (SDS : 5.10–4 M, 0.5%
Ethanol, pH : 8, Airflow rate : 50 mL/min.)
4.6. Selective Flotation

In this part of the study, metal ions were floated selectively when they are
present together. Metal solutions contained copper, zinc, chromium and silver. The
results were presented for different compositions of metal solutions in Figures 4.36,
4.37 and 4.38 in the presence of 5.10–4 M SDS with varying ethanol amount and pH.
In order to separate the metals from each other, three different flotation
experiments were performed. The first flotation experiment was done to separate copper
from chromium, zinc and silver solution. The first solution was prepared by using the
condition that had given the best recovery of copper ( 5.10-4 M SDS, 0.5% of ethanol
and pH value of 10).
As it is seen in Figure 4.36, when silver was present in the solution of copper
(10 mg/L), zinc (10 mg/L) and chromium (10 mg/L), small amount of silver precipitated
as silver chloride and separated selectively. The rest remained in the cell due to its very
low flotability (30%). So copper and chromium were separated from zinc and silver.
The recoveries of copper and chromium floated was 77% and 81%. The recovery of
zinc was only 45%. This shows one that zinc can not be removed separately.

80
Metal Recovery, %

60

Cu
40 Cr
Ag
Zn

20 SDS : 5.10-4M, 0.5% Ethanol

pH = 10
Airflow rate : 50ml/min.

0
20 40 60 80

Water Recovery, %

59
Figure 4.36. Selectivity Results of Copper, Zinc, Silver and Chromium. (SDS: 5.10–4 M,
0.5% Ethanol, pH : 10, Initial Metal Concentration (Cu, Cr, Zn, Ag) : 10
mg/L)
The second flotation experiment was connected to separate chromium from
copper and zinc solution and the result is given in Figure 4.37. The pH of the solution
was equal to 8. The initial metal concentrations were 10 mg/L for each of them. The
recoveries obtained were 86%, 60% and 58% for chromium, zinc and copper,
respectively. This shows the possibility that chromium separation from the solution that
has zinc and copper under this conditions.

80
Metal Recovery, %

60

40
Cu
Cr
Zn
20
SDS : 5.10-4M, 0.5% Ethanol
pH = 8, C metal =10ppm
Air Flowrate : 50ml/min.
0
20 40 60 80

Water Recovery, %

Figure 4.37. Selectivity Results of Copper, Zinc and Chromium. (SDS : 5.10–4 M, 0.5%
Ethanol, pH : 8, Initial Metal Concentration : 10 mg/L)

The third flotation experiment was performed to separate zinc from the solution
mixture of copper and chromium. In this case the conditions were different. Changing
the pH and the ethanol concentration as 4 and 0.1%, respectively made the separation
possible. The recoveries were 72% for zinc, 31% for chromium and 27% for copper. As
seen in Figure 4.38, the selective flotation of Zn is possible under these conditions.
Because this is the best condition for zinc not for others.

60
 80

60
Metal Recovery, %

40

Cu
Cr
Zn
20
SDS : 5.10-4M, 0.1% Ethanol
pH = 4, C metal =10ppm
Air Flowrate : 50ml/min.
0
20 40 60 80

Water Recovery, %

Figure 4.38. Selectivity Results of Copper, Zinc and Chromium. (SDS : 5.10–4 M, 0.1%
Ethanol, pH : 4, Initial Metal Concentration : 10 mg/L)

4.7. Kinetic Studies of Metals

The curve fitting results of the flotation kinetics equations are given in Figures
4.39 and 4.40 for the case of best recoveries for Cu, Zn and Cr. A number of kinetic
equations were fitted the data to determine the best phenomenological model and these
equations are given in Table 4.2 (Polat and Chander, 2003). The classical first order
model (Panu, et. al, 1976) describes the hydrophobic particles flotation having a
constant flotability (Eqn. 4.5). For the case of a monodisperse feed, where all particles
have the same flotability, the equation is expressed by:

R(t ) = R∞ (1 − e −kt ) (4.5)

where R is the recovery at time t, R* is the ultimate recovery for an infinite time,
and k is the rate constant.
It was observed that the classical first order equation fitted the data as good and
better than any of the other equations in Table 4.2. hence the results given in Figures
4.39 and 4.40 are for the Classical First-Order Flotation Kinetics Equation. It can be
seen from the Figure 4.39 that Zn floats not only more in amount but also floats faster

61
than Cu since its flotation rate (0.120 min-1) is almost twice as large as that of Cu (0.059
min-1 ).
The fact that the Classical First-Order Flotation Kinetics Equation fitted the data
better than other equations means that the floatable species of copper and zinc in
solution have flotation probability similar to each other for each ion. That is, all the
copper ions in solution show similar floatability to other copper ions whereas all the
zinc ions are similar to the other zinc ions in solution. Even though this seems not
suprising, it is an indirect indication that surfactant-ion pairs are similar and show
similar flotability for the case of each ion-surfactant pair.
Another important observation that somehow flotation of zinc and chromium
seem to follow the first-order kinetics when compared to copper. This may have several
reasons such as a faster and better interaction of the zinc and chromium ions with the
surfactant which results in a rapid surfactant-ion pair which than interacts in a first-
order fashion with the air bubbles. If the surfactant-ion interactions were slower
compared to the flotation rate, then secondary effects would play a role and the flotation
process would not follow a first-order rate equation as was the case for copper.
However, the data is not sufficient to speculate further on such behaviour.
Standart errors and R2 values were also determined for copper, zinc and
chromium. R2 values were obtained as 0.9913, 0.9995 and 0.9916 and standart errors
were determined as 0.0282, 4.27. 10-3 and 0.0205 for copper, zinc and chromium,
respectively.

62
 100
R=100(1-e-kt)
kCu=0.0589 min-1

Cumulative Recovery, %
80 kZn=0.1217 min-1

60

40

Copper
20
Zinc

0
0 5 10 15 20

Time, minutes

Figure 4.39. The Results of the Flotation Kinetics for Copper and Zinc

100
-kt
R = 100(1-e )
-1
k Cr = 0,2238 min
80
Cumulative Recovery, %

60

40

20

0
2 4 6 8 10 12 14 16

Time, min.

Figure 4.40. The Results of the Flotation Kinetics for Chromium.

63
Table 4.2. The First-Order Models with Distribution of Flotation Rate Constants Tested
for the Cu and Zn Recovery.

Model 1 - R(t) / 100

Classical First-Order Equation e −Kt
wt wt
First-Order Equation with Rectangular − µt + − µt −
e 2 −e 2
Distribution of Flotation Rates
wt
wt wt
First-Order Equation with Triangular −
e 2+e 2 −2
Distribution of Flotation Rates wt
e − µt ( )2
2
First-Order Equation with Sinusoidal − µt +
2wt
2w t − µt −
2wt
e 3 − e 6
Distribution of Flotation Rates π
2w t
1+( )2
π
First-Order Equation with Gamma µ2
µ + σ 2t − σ 2
Distribution of Flotation Rates ( )
µ
First-Order Equation with Normal µ µ
σt + σt −
Distribution of Flotation Rates erf( σ ) − erf( σ )
2 2
σ 2 t2
µt −
2e 2

64
 CHAPTER 5

CONCLUSIONS

In this study, ion flotation experiments were performed to investigate the

removal of heavy metals (copper, zinc, silver and chromium) from wastewaters.
Various parameters such as pH, surfactant and frother concentrations and airflow rate
values were tested to determine the optimum flotation conditions. Sodium dodecyl
sulfate (SDS) and Hexadecyltrimethyl ammonium bromide (HTAB) were used as
collectors depending on the charge of metal species which changes as a function of
solution pH. Ethanol / MIBC were used as frothers. Based on the findings of these
studies, the following main conclusions can be obtained:

1. For 10 mg/L copper, the recovery was obtained as 73.6% in the case of
0.5% ethanol and 5.10–4 M SDS concentration at pH 4. For 50 mg/L
copper, the recovery decreased to 41.8% due to insufficient number of
surfactant molecules present. For different pH values, especially pH of
10, the recovery increased to 89.5%. At pH of 12, instead of SDS, HTAB
was used as cationic surfactant (because of the negative charge of
copper) and the recovery was obtained 79.0%. At pH of 10 HTAB had
no effect on copper recovery (48.2%).

2. For 10 mg/L zinc, the highest recovery was obtained as 68.9% in

–4
presence of 0.1% ethanol and 5.10 M SDS concentration at pH 4. For
50 mg/L zinc, the recovery decreased to 41.4%. It can be explained that
the number of surfactant molecules (30.1x1019). For pH values as 6 and
8, the recoveries of 68,2% and 70,6% were obtained respectively. At pH
10 and 12, the cationic surfactant, HTAB was used. In the case of pH 12
the recovery was 72.3%. while it was low in the case of pH 10.

3. For 10 mg/L silver, the varying ethanol concentrations had no influence

on the silver flotation for all the pH range. Another type of frother
known as methly isobutly carbinol (MIBC) was used and the highest
recovery was obtained as 72.5% in the case of 10-4 M SDS, 0.1% of

65
 MlBC and pH 4. For 100 mg/L silver, the recovery decreased to 41.3%
depending on the high number of silver ions (5.58x1020) compared to the
surfactant molecules (30.1x1019). Increasing pH values did not affect the
silver recoveries and the best recovery was at pH 4. At pH 12, HTAB
was used and the recovery was 71.3%. When HTAB was used at pH 10,
the recovery decreased because of the positive charge of silver.
4. The recovery of chromium was low at pH of 4 for several different
concentrations of SDS and ethanol. The best recovery was obtained at
pH 8 (96.8%). At pH 12, HTAB was used and the recovery was 86.1%.
At pH 10, HTAB had no effect on the recovery.
5. Increasing the ionic strength of water decreased the recoveries most
probably due to the presence of excess Na, Mg, Ca ions that competed
with metals for surfactant molecules.
6. Selective flotation experiments were also conducted in the presence of
metal ion mixture solutions. It was possible to separate copper and
chromium from zinc and silver under suitable conditions. However, zinc
could not be removed separately. It was also possible to separate
chromium from zinc and copper and zinc from copper and chromium
under suitable conditions.
7. The classical first order equation fitted the results. Zinc and chromium
floated not only more in an amount but also floated faster than copper
since their flotation rates (0.120 min-1 and 0.224 min -1) were almost
twice as large as that of copper (0.059 min-1).
8. MIBC was more effective to decrease surface tension at air/water
interface compared to ethanol. The surface tension data was used to
calculate the area (25.3 Ao2) that one SDS molecule occupies art
air/water interface.

66
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Panu, H., Danalache, E., Cojocariu, D.G., 1976. Mathematical Models of Patch and
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70
 APPENDIX A

SURFACE TENSION

Table A.1 Surface Tension Values of Sodium Dodecyl Sulfate (SDS).

Surface Surface Surface

SDS SDS SDS
Tension Tension Tension
Concentration Concentration Concentration
(dyn/cm) (dyn/cm) (dyn/cm)
71,3 0,0002 56,3 0,003 38,46 0,011
70,48 0,0004 55,6 0,0032 38,46 0,012
69,6 0,0006 51,7 0,004 38,46 0,0135
69,3 0,0008 47,12 0,005 38,46 0,014
67,9 0,001 43,8 0,006 38,46 0,0155
66,15 0,00142 41,3 0,007 38,46 0,0168
64,4 0,00175 39,04 0,008 38,46 0,0179
62,5 0,002 38,46 0,01 38,46 0,019
59,8 0,00236 38,46 0,0104 38,46 0,021

71
 APPENDIX B

FORMS OF METALS IN WATER

Forms of Copper (10 – 50 mg/L) in Water

Table B.1. Speciation Table of 10 mg/L Copper in Water as a Function of pH.

pH Cu(OH)2 Cu(OH)3- Cu(OH)42- Cu2+ Cu2(OH)22+ Cu2OH3+ Cu3(OH)42+ CuOH+

2 8,7224E-17 1,86E-25 1,65E-36 1,574E-04 5,466E-15 4,1E-12 4,769E-25 4,5E-10

3 8,7249E-15 1,86E-22 1,66E-32 1,574E-04 5,467E-13 4,1E-11 4,771E-21 4,5E-09

4 8,7228E-13 1,86E-19 1,65E-28 1,573E-04 5,464E-11 4,09E-10 4,768E-17 4,5E-08

5 8,6995E-11 1,85E-16 1,65E-24 1,569E-04 5,435E-09 4,07E-09 4,729E-13 4,49E-07

6 8,4226E-09 1,79E-13 1,6E-20 1,519E-04 5,095E-07 3,82E-08 4,292E-09 4,35E-06

7 4,5724E-07 9,74E-11 8,67E-17 8,25E-05 1,502E-05 1,12E-07 6,867E-06 2,36E-05

8 3,6912E-06 7,87E-09 7E-14 6,66E-06 9,785E-06 7,33E-09 3,613E-05 1,9E-05

9 1,796E-05 3,83E-07 3,41E-11 3,24E-07 2,316E-06 1,73E-10 4,16E-05 9,27E-06

10 6,868E-05 1,46E-05 1,3E-08 1,24E-08 3,387E-07 2,54E-12 2,327E-05 3,54E-06

11 4,979E-05 1,061E-04 9,45E-07 8,98E-11 1,78E-09 1,33E-15 8,866E-08 2,57E-07

12 6,5004E-06 1,385E-04 1,23E-05 1,17E-13 3,035E-13 2,27E-20 1,973E-12 3,35E-09

13 3,8968E-07 8,3E-05 7,39E-05 7,03E-17 1,091E-17 8,17E-26 4,251E-18 2,01E-11

72
 Table B.2 Speciation Table of 50 mg/L Copper in Water as a Function of pH.

pH Cu(OH)2 Cu(OH)3- Cu(OH)42- Cu2+ Cu2(OH)22+ Cu2OH3+ Cu3(OH)42+ CuOH+

2
4,361E-16 9,292E-25 8,271E-36 7,868E-04 1,366E-13 1,024E-10 5,960E-23 2,251E-09
3
4,362E-14 9,296E-22 8,276E-32 7,868E-04 1,367E-11 1,024E-09 5,964E-19 2,251E-08
4
4,361E-12 9,294E-19 8,274E-28 7,866E-04 1,366E-09 1,023E-08 5,959E-15 2,250E-07
5
4,348E-10 9,265E-16 8,248E-24 7,841E-04 1,357E-07 1,017E-07 5,903E-11 2,243E-06
6
4,094E-08 8,724E-13 7,766E-20 7,383E-04 1,204E-05 9,015E-07 4,928E-07 2,112E-05
7
1,150E-06 2,451E-10 2,182E-16 2,074E-04 9,496E-05 7,113E-07 1,092E-04 5,933E-05
8
6,765E-06 1,442E-08 1,283E-13 1,220E-05 3,287E-05 2,462E-08 2,224E-04 3,490E-05
9
3,223E-05 6,869E-07 6,115E-11 5,814E-07 7,462E-06 5,590E-10 2,406E-04 1,663E-05
10
1,411E-04 3,007E-05 2,677E-08 2,545E-08 1,430E-06 1,071E-11 2,018E-04 7,281E-06
11
2,399E-04 5,113E-04 4,552E-06 4,327E-10 4,134E-08 3,097E-14 9,920E-06 1,238E-06
12
3,250E-05 6,927E-04 6,166E-05 5,862E-13 7,587E-12 5,683E-19 2,467E-10 1,677E-08
13
1,948E-06 4,152E-04 3,697E-04 3,514E-16 2,727E-16 2,042E-24 5,314E-16 1,005E-10

8e-4
Cu2+ Cu(OH)-3

6e-4
Concentration, mg/L

4e-4

Cu3(OH)42+
Cu(OH)2
2e-4 Cu(OH)2-4

CuOH+ Cu2(OH)22+

0
2 4 6 8 10 12

pH

Figure B.1 Forms of Copper (50 mg/L) in Water as a Function of pH

73
Forms of Zinc (10 – 50 mg/L) in Water

Table B.3 Speciation Table of 10 mg/L Zinc in Water as a Function of pH.

pH Zn(OH)2 Zn(OH)3- Zn(OH)42- Zn2+ ZnOH+

2 2,130E-18 1,114E-26 4,970E-37 1,530E-04 1,384E-11
3 2,131E-16 1,115E-23 4,973E-33 1,530E-04 1,384E-10
4 2,131E-14 1,115E-20 4,973E-29 1,530E-04 1,384E-09
5 2,130E-12 1,115E-17 4,973E-25 1,530E-04 1,384E-08
6 2,129E-10 1,114E-14 4,969E-21 1,528E-04 1,383E-07
7 2,111E-08 1,104E-11 4,928E-17 1,516E-04 1,371E-06
8 1,929E-06 1,009E-08 4,503E-13 1,385E-04 1,253E-05
9 6,322E-05 3,307E-06 1,476E-09 4,539E-05 4,106E-05
10 9,575E-05 5,009E-05 2,235E-07 6,875E-07 6,220E-06
11 2,364E-05 1,237E-04 5,518E-06 1,697E-09 1,536E-07
12 1,996E-06 1,044E-04 4,658E-05 1,433E-12 1,296E-09
13 5,352E-08 2,800E-05 1,249E-04 3,843E-16 3,476E-12

74
Table B.4. Speciation Table of 50 mg/L Zinc in Water as a Function of pH.

pH Zn(OH)2 Zn(OH)3- Zn(OH)42- Zn2+ ZnOH+

2 1,065E-17 5,570E-26 2,485E-36 7,649E-04 6,918E-11
3 1,065E-15 5,572E-23 2,486E-32 7,649E-04 6,919E-10
4 1,065E-13 5,573E-20 2,486E-28 7,649E-04 6,919E-09
5 1,065E-11 5,572E-17 2,486E-24 7,648E-04 6,919E-08
6 1,064E-09 5,568E-14 2,484E-20 7,642E-04 6,913E-07
7 1,056E-07 5,522E-11 2,464E-16 7,579E-04 6,856E-06
8 9,645E-06 5,046E-08 2,251E-12 6,925E-04 6,265E-05
9 3,161E-04 1,654E-05 7,378E-09 2,270E-04 2,053E-04
10 4,788E-04 2,505E-04 1,118E-06 3,438E-06 3,110E-05
11 1,182E-04 6,183E-04 2,759E-05 8,487E-09 7,678E-07
12 9,978E-06 5,220E-04 2,329E-04 7,165E-12 6,482E-09
13 2,676E-07 1,400E-04 6,246E-04 1,922E-15 1,738E-11

8e-4

Zn2+
Zn(OH)-3
6e-4
Concentration, mg/L

Zn(OH)2

4e-4

Zn(OH)2-4

2e-4

ZnOH+

0
4 6 8 10 12

pH

Figure. B.2. Forms of Zinc (50 mg/L) in Water as a Function of pH

75
Forms of Silver (10 – 100 mg/L) in Water

Table B.5. Speciation Table of 100 mg/L Silver in Water as a Function of pH.

pH Ag(OH)2- Ag+ AgOH (aq) pH Ag(OH)2- Ag+ AgOH (aq)

2 9,182E-24 9,271E-04 9,004E-14 8 9,184E-12 9,270E-04 9,004E-08

3 9,185E-22 9,271E-04 9,005E-13 9 9,176E-10 9,262E-04 8,997E-07

4 9,185E-20 9,271E-04 9,005E-12 10 9,096E-08 9,181E-04 8,918E-06

5 9,185E-18 9,271E-04 9,005E-11 11 8,297E-06 8,374E-04 8,135E-05

6 9,185E-16 9,271E-04 9,005E-10 12 3,101E-04 3,130E-04 3,040E-04

7 9,185E-14 9,271E-04 9,005E-09 13 8,366E-04 8,444E-06 8,202E-05

1e-3

Ag+
8e-4
Ag(OH)2-
Concentration, mg/L

6e-4

4e-4

2e-4 AgOH

0
6 8 10 12

pH

Figure B.3. Forms of Silver (100 mg/L) in Water as a Function of pH

76
 Table B.6. Speciation Table of 10 mg/L Silver in Water as a Function of pH.

pH Ag(OH)2- Ag+ AgOH (aq) pH Ag(OH)2- Ag+ AgOH (aq)

2 9,18E-25 9,27E-05 9,23E-15 8 9,1847E-13 9,27E-05 9,23E-09

3 9,19E-23 9,27E-05 9,23E-14 9 9,1764E-11 9,26E-05 9,22E-08

4 9,19E-21 9,27E-05 9,23E-13 10 9,0942E-09 9,18E-05 9,14E-07

5 9,19E-19 9,27E-05 9,23E-12 11 8,2795E-07 8,36E-05 8,32E-06

6 9,19E-17 9,27E-05 9,23E-11 12 3,0761E-05 3,1E-05 3,09E-05

7 9,19E-15 9,27E-05 9,23E-10 13 9,1847E-13 9,27E-05 9,23E-09

77
Forms of Chromium (10 – 50 mg/L) in Water

Table B.7. Speciation Table of 10 mg/L Chromium in Water as a Function of pH.

pH Cr(OH)2+ Cr(OH)3 Cr(OH)4- Cr3+ Cr2(OH)24+ Cr3(OH)45+ CrO2- CrOH2+

2 1,235E-10 5,320E-15 1,912E-24 1,137E-04 1,203E-09 2,432E-15 2,218E-24 2,560E-06

3 1,029E-08 4,435E-12 1,594E-20 9,475E-05 8,359E-08 1,408E-11 1,849E-20 2,133E-05

4 3,795E-07 1,635E-09 5,878E-17 3,494E-05 1,136E-06 7,059E-09 6,817E-17 7,866E-05

5 4,934E-06 2,126E-07 7,642E-14 4,542E-06 1,921E-06 1,552E-07 8,864E-14 1,023E-04

6 3,226E-05 1,390E-05 4,997E-11 2,970E-07 8,211E-07 4,336E-07 5,795E-11 6,686E-05

7 2,107E-05 9,081E-05 3,264E-09 1,940E-09 3,504E-09 1,209E-09 3,785E-09 4,368E-06

8 2,634E-06 1,135E-04 4,079E-08 2,424E-12 5,473E-13 2,359E-14 4,731E-08 5,459E-08

9 2,671E-07 1,151E-04 4,137E-07 2,459E-15 5,630E-17 2,462E-19 4,798E-07 5,536E-10

10 2,503E-08 1,079E-04 3,877E-06 2,304E-18 4,944E-21 2,026E-24 4,497E-06 5,188E-12

11 1,519E-09 6,545E-05 2,353E-05 1,398E-21 1,820E-25 4,526E-30 2,729E-05 3,148E-14

12 3,079E-11 1,327E-05 4,769E-05 2,834E-25 7,480E-31 3,770E-37 5,531E-05 6,381E-17

13 3,431E-13 1,479E-06 5,315E-05 3,159E-29 9,290E-37 5,218E-45 6,164E-05 7,112E-20

78
 Table B.8. Speciation Table of 50 mg/L Chromium in Water as a Function of pH.

pH Cr(OH)2+ Cr(OH)3 Cr(OH)4- Cr3+ Cr2(OH)24+ Cr3(OH)45+ CrO2- CrOH2+

2 6,173E-10 2,660E-14 9,558E-24 5,685E-04 3,008E-08 3,039E-13 1,109E-23 1,280E-05

3 5,117E-08 2,205E-11 7,925E-20 4,711E-04 2,066E-06 1,731E-09 9,192E-20 1,061E-04

4 1,765E-06 7,605E-09 2,733E-16 1,625E-04 2,458E-05 7,101E-07 3,170E-16 3,658E-04

5 2,098E-05 9,041E-07 3,250E-13 1,932E-05 3,474E-05 1,193E-05 3,769E-13 4,349E-04

6 1,322E-04 5,696E-05 2,047E-10 1,217E-06 1,379E-05 2,983E-05 2,375E-10 2,740E-04

7 1,053E-04 4,536E-04 1,630E-08 9,690E-09 8,742E-08 1,506E-07 1,891E-08 2,182E-05

8 1,317E-05 5,674E-04 2,040E-07 1,212E-11 1,368E-11 2,949E-12 2,366E-07 2,729E-07

9 1,336E-06 5,755E-04 2,069E-06 1,230E-14 1,407E-15 3,077E-17 2,399E-06 2,768E-09

10 1,252E-07 5,393E-04 1,939E-05 1,152E-17 1,236E-19 2,532E-22 2,248E-05 2,594E-11

11 7,595E-09 3,273E-04 1,176E-04 6,991E-21 4,551E-24 5,658E-28 1,364E-04 1,574E-13

12 1,540E-10 6,634E-05 2,384E-04 1,417E-24 1,870E-29 4,713E-35 2,766E-04 3,191E-16

13 1,716E-12 7,393E-06 2,657E-04 1,579E-28 2,323E-35 6,523E-43 3,082E-04 3,556E-19

6e-4

Cr3+ Cr(OH)3
5e-4
CrOH2+
Concentration, mg/L

4e-4

CrO-2
3e-4

Cr3(OH)5+4
2e-4
Cr2(OH)4+2 Cr(OH)-4

1e-4 Cr(OH)+2

0
2 4 6 8 10 12

pH

Figure B.4. Forms of Chromium (50 mg/L) in Water as a Function of pH

79
 APPENDIX C

CALCULATION OF FLOTATION RESULTS

Calculation part of the results of the highest recoveries are explained in details in
the following tables.

Table C.1. Calculation of the Highest Recovery of Zinc. ( Zn : 10mg/L, pH:4, 5.10 –4 M
SDS and 0.1% ethanol)

Time Weight Weight Zn Zn Zn Rec. Cum Zn Cum. Cum. Zn Cum.

Weight Zn
minutes gram % ppm units % units % % Rec. %
2 39 3,9 16,73 65,25 7,6 65,25 3,9 16,7 7,6
4 50 5,0 16,73 83,65 9,8 148,90 8,9 16,7 17,4
8 100 10,0 15,19 151,90 17,7 300,80 18,9 15,9 35,1
16 225 22,5 12,88 289,80 33,8 590,60 41,4 14,3 68,9
Waste 586 58,6 4,55 266,63 31,1 857,23 100,0 8,6 100,0
Total 1000 100,0 857,23 100,0

Table C.2. Calculation of the Highest Recovery of Silver. (Ag : 10mg/L, pH:4, 10 –4 M
SDS and 0.1% MIBC)

Time Weight Weight Ag Ag Ag Cum Ag Cum. Cum. Ag Cum. Ag

Rec. Weight
minutes gram % ppm units % units % % Rec. %
2 37 3,7 37,21 137,68 13,5 137,68 3,7 37,2 13,5
4 58 5,8 33,18 192,44 18,9 330,12 9,5 34,7 32,3
8 100 10,0 26,28 262,80 25,7 592,92 19,5 30,4 58,1
16 150 15,0 9,83 147,45 14,4 740,37 34,5 21,5 72,5
Waste 655 65,5 4,28 280,34 27,5 1020,71 100,0 10,2 100,0
Total 1000 100,0 1020,71 100,0

80
Table C.3. Calculation of the Highest Recovery of Chromium. ( Cr : 10mg/L, pH:8,
5x10 –4 M SDS and 0.5% Ethanol)

Time Weight Weight Cr Cr Cr Rec. Cum Cr Cum. Cum. Cum.

Weight Cr Cr
minutes gram % ppm units % units % % Rec. %
2 59 5,9 43,50 256,65 25,4 256,65 5,9 43,5 25,4
4 61 6,1 31,19 190,26 18,9 446,91 12,0 37,2 44,3
8 90 9,0 22,80 205,20 20,3 652,11 21,0 31,1 64,6
16 205 20,5 15,55 318,78 31,6 970,88 41,5 23,4 96,2
Waste 585 58,5 0,650 38,03 3,8 1008,91 100,0 10,1 100,0
Total 1000 100,0 1008,91 100,0

Table C.4. Calculation of the Highest Recovery of Copper (Cu : 10mg/L, pH:10, 5.10 –4
M SDS and 0.5% Ethanol)

Time Weight Weight Cu Cu Cu Rec. Cum Cu Cum. Cum. Cum.

Weight Cu Cu
Minutes Gram % ppm Units % Units % % Rec. %
(a) (b) (c) (d) (e) (f) (g) (h) (k) (l)
2 45 4,5 37,86 170,37 18,6 170,37 4,5 37,9 18,6
4 51 5,1 28,18 143,72 15,7 314,09 9,6 32,7 34,2
8 135 13,5 19,38 261,63 28,5 575,72 23,1 24,9 62,7
16 250 25,0 9,83 245,75 26,8 821,47 48,1 17,1 89,5
Waste 519 51,9 1,85 96,02 10,5 917,48 100,0 9,2 100,0
Total 1000 100,0 917,48 100,0

81
 To calculate the results of AAS analysis Table C. series were used. In Tables
C.1, C.2, C.3 and C.4, first column expresses the time, second column shows the
amount of foam, fourth one is the results of AAS analysis. These calculations depend on
the mass balance equation. It means the results of addition of weight percents at
different time multiply with amount of copper (mg/L), equals to the initial copper
concentration (10ppm). Calculations are explained in the following parts:
(c) = Weight*100 / Total Weight
(e) = Weight %* (d)
(f) = Metal Units* 100 / Total Metal Units
(g)= Cumulative Metal Units
(h)= Cumulative Weight Units
(k)= Cumulative Metal Units / Cumulative Weight Units
(l)= Total Metal Recovery

82