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ACKNOWLEDGMENT
Also, I would like to thank the many persons who in one way or another
have participated in the completion of this work; particularly I appreciate the
efforts of: Prof. Dr. Abbas H. Sulaymon the head Environmental
Engineering Department, University of Baghdad for his encouragement and
providing the research facilities and all the staff of Environment Engineering
Department for their help and assistance throughout the research.
I
REMOVAL OF COPPER ION FROM
WASTE WATER BY FLOTATION
By
Farah Ibrahim Abed
Supervised by
Ass. Prof. Dr. Ahmed A. Mohammed
Environmental Engineering Department-College of Engineering
University of Baghdad
Abstract
II
Abstract
It was found that the presence of NaCl in the solution reduced the
recoveries since the presence of excess Na+ ions compete with metal and the
metal ions cannot find enough surfactant molecules to attach to. Adding
ethanol at 1% concentration increased the removal efficiency. From the
results the rate of flotation was found to be first order.
III
CONTENTS
Acknowledgment .................................................................................................... I
Abstract .....................................................................................................II
Contents ................................................................................................... IV
List of Figures..VI
List of Tables... VIII
Nomenclature ............................................................................................ X
Chapter One Introduction ......................................................................1
1.1 Statement of Pollution Problem ..............................................................1
References ................................................................................................ 59
Appendix .................................................................................................. 71
V
List of Figures
Figure 2.1 Typical ion flotation process. 10
Figure 2.4 flow chart showing how ion flotation with dodecyl sulfate and
electrolytic metal recovery could be used to remove residual metal ions
from a process effluent.25
Figure 3.1Schematic diagram of the experimental set-up...38
Figure 3.2 Experimental set-up of the flotation column used in the present
study .38
Figure 4.7 Effect of copper concentration on the removal rate (pH=10; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm).47
VI
Figures
Figure 4.8 Effect of copper concentration on the removal rate (pH=4; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm)47
Figure 4.9 Effect of gas flow rate on the removal rate of copper (pH=4;
Co=25 mg/l; SDS=350 mg/l; ethanol=1%,do=1mm)49
Figure 4.10 Effect of gas flow rate on the removal rate of copper (pH=10;
Co=100 mg / l; SDS=75 mg/l; ethanol=1%,do=1mm).49
Figure 4.11 Effect of hole diameter of the gas distributor on the removal
rate of copper(pH=4;Co=25mg/l;SDS=350mg/l; Q=250ml/min; ethanol = 1
% )..51
VII
List of Tables
Table 1.1Copper levels reported in industrial waste waters .3
Table 10 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=10,
Co =100 mg/l, SDS=75 mg/l, Ethanol=1%, do=1mm..74
VIII
Tables
Table 11 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=4, Co
=25 mg/l, SDS=350 mg/l, Ethanol=1%, do=1mm74
Table 16 Effect of hole diameter of the gas distributor on the removal rate of
copper, pH=4, Co=25 mg/l, SDS=350 mg/l, Q=250 ml/min,
Ethanol=1%...................................................................................................77
IX
NOMENCLATURE
Symbol Units
Co Initial copper concentration mg/l
C Residual copper concentration mg/l
CMC Carboxymethyl cellulose -
db Bubble diameter m
do Hole diameter mm
DAF Dissolved air flotation -
g Acceleration due to gravity m/s2
H Bed height m
HDS High dodecyl sulfate -
HTAB Hexadecyltrimethyl ammonium bromide -
IAF Induced air flotation -
k Rate constant min-1
n order of flotation equation -
Q Gas flow rate ml/min
R Recovery -
Sb bubble surface area cm2
SDS Sodium dodecylsulfate -
ug Interstitial gas velocity m/s
Chapter One
INTRODUCTTON
Chapter One
Introduction
Chapter One
Introduction
Table 1.2 EPA regulations for industrial effluents pollution of surface waters
(Misra, 1995)
Substances Limits(mg/l)
Copper 1
Sliver 0.2-2g/l
Chromium 0.5
Zinc 5
1.2 Harmful Effects of Heavy Metals
Industrial activity is the main culprit behind most environmental
pollution problems and ecosystem damage, coming from the accumulation
of pollutants such as toxic metals chromium, copper, lead, cadmium, zinc,
etc. (Pino et al., 2006).Contamination of soils, groundwater, surface water
Chapter One
Introduction
and air with hazardous and toxic chemicals poses significant problems for
both human health and the environment (Ansari et al., 2007). In view of the
human health impacts, each metal imparts different effects and symptoms.
For example, copper is an essential element but can cause adverse health
effects. The safe and adequate copper intake is 1.5 to 3 mg/day (National
Research Council, 1989); however, at high doses, copper can cause acute
effects, such as astrointestinal (GI) disturbances, damage to the liver and
renal systems, and anemia. (Letterman et al., 1999).Health effects of Cu, Pb,
Cd and Ni were given in Table 1.3.
2.1.2 CoagulationFlocculation
Coagulationflocculation can be employed to treat wastewater laden with
heavy metals. Principally; the coagulation process destabilizes colloidal
particles by adding a coagulant and results in sedimentation (Shammas et al.,
2004).To increase the particle size, coagulation is followed by the
flocculation of the unstable particles into bulky floccules (Semerjian
and Ayoub, 2003).In spite of its advantages, coagulationflocculation has
Limitations such as high operational cost due to chemical consumption. The
increased volume of sludge generated from coagulationflocculation may
hinder its adoption as a global strategy for wastewater treatment. This can be
attributed to the fact that the toxic sludge must be converted into a stabilized
product to prevent heavy metals from leaking into the environment. To
overcome such problems, electro-coagulation may be a better alternative
than the conventional coagulation, as it can remove the smallest colloidal
particles and produce just a small amount of sludge. However, this technique
also creates a floc of metallic hydroxides, which requires further
purification, making the recovery of valuable heavy metals impossible
(Ayoub et al., 2001).
Chapter One
Introduction
heavy metals from the rinse water such as for the removal of nickel, copper,
tin, aluminum anodizing and zinc ions (Seneviratne, 2006).
It is a reversible chemical reaction where ions in a feed stream are
exchanged for similarly charged ions on the surface of a solid ion exchange
resin. Once capacity of the resin is reached (most ions of the resin are
exchanged), the resin is taken out of service for regeneration. The
performance and economics of ion exchange are related to the capacity of
resin (Eckenfelder, 2009).
2.1.5 Electrodialysis
In the electrodialysis process, ionic components of a solution are
separated through the use of semi permeable ion-selective membranes. This
process may be operated in either a continuous or a batch mode. Among the
technical problems associated with the electrodialysis process, concentration
polarization is perhaps the most serious. Other problems in practical
applications include membrane scaling by inorganic in feed solutions as well
as membrane fouling by organics (Nicholas, 2002).
Chapter One
Introduction
2.1.6 Adsorption
Adsorption is a physical process where soluble molecules (adsorbate) are
removed by attachment to the surface of a solid substrate (absorbent)
primarily by Vander Waals forces, although chemical or electrical attraction
may also be important. Adsorbents must have a very high specific surface
area and include activated alumina, clay colloids, hydroxides and adsorbent
resins, with the most widely used being activated carbon. Activated carbon
can be very effective in removing metal ions from wastewater by first
chelating the metal ions with an organic chelant, such as citric acid or
EDTA. When the chelated mixture treated using activated carbon, the
organic chelant will adsorb to the carbon, removing the chelated metals
along with it (Woodard, 2006). Although, adsorption has been well
established as a technology for removing toxic compounds from wastes or
wastewaters (Zouboulis et al., 1994), the process may face filter-blocking
problems (Ghazy et al., 2008).
2.2 Flotation
Flotation as a separation process has recently received a considerable
interest owing to its simplicity, rapidity, economy, good separation yields
(Recovery> 95 % for small impurity agent concentrations (10-610-2 mol.L-1)
,a large possibility of application for species having different nature and
structure, flexibility and friability of equipment and processing for recovery
purpose and production of more concentrated sludge, occupying smaller
volumes(Matis, 1995; Stoica et al., 1998; Voronin and Dibrov, 1999;
Pacheco and Torem, 2002; Rubio et al., 2002; Matis et al., 2004; Medina
et al., 2005; Rosa and Rubio, 2005; Carissimi and Rubio, 2005). It is
believed that this process will be soon incorporated as a clean technology to
Chapter One
Introduction
Chapter Two
Literature Survey
Air flotation has been applied to the separation of heavy metal from water
; the operation may be classified in to: (1) Dissolved air flotation, and (2)
Induced air flotation with respect to the generation of fine bubbles. In
IAF(Induced air flotation )bubbles are generated by passing the gas through
some kind of disperser: porous media, perforated tubes (spargers), impeller,
etc. Bubble diameter is in order of 1000m.In DAF bubbles are produced
when the pressure of super saturated solution is lowered to atmospheric
pressure and this is done by saturating the liquid at high pressure and
releasing the pressure. Bubble sizes are small, ranging from 30 t0 120 m
(Lawrence et al., 2010).
Chapter Two
Literature Survey
Induced air flotation has low retention times while dissolved air flotation
are higher (20-60min).So that, dissolved air flotation is inefficient when the
treatment of high volumes effluents and high flow rates is required
(Mohammed , 2004).
In general, the DAF process can provide the highest treatment efficiency.
However, DAF process has some limitations in terms of investment
cost, complex operations and equipment size (Painmanakul et al., 2010).
Therefore, IAF process is an attractive alternative and chosen for this study.
Column flotation is still a subject of great interest in mineral processing
with a steadily growing number of research studies and industrial
applications (Rubinstein, 1994; Finch, 1995). Applications of column
flotation in the field of recovery of heavy metals (Filippov and Filippova,
2003) have been reported.
Some of the advantages claimed with flotation columns include
improved separation performance, particularly for fine materials; low
capital and operating costs; low plant floor space requirements;
and easy adaptability to automatic control. Flotation columns are being
used in iron ore, copper, lead, zinc, chromium, cadmium, and coal
flotation applications and are expected to become even more popular
because their simplicity in construction and flexibility of operation (Perry et
al., 1997).
Chapter Two
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Chapter Two
Literature Survey
2.4 Surfactant
A surfactant (a contraction of the term surface-active agent) is a substance
that, when present at low concentration in a system, has the property of
adsorbing in to the surface or interfaces of the system and altering to a
marked degree the surface or interface free energies of those surfaces (or
interface).The term interface indicates a boundary between any two
immiscible phases; the term surface denotes an interface where one phase is
a gas, usually air (Rosen, 1989).
Surface-active agents have a characteristic molecular structure consisting
of a structural group that has very little attraction for the solvent, known as
a lyophobic group, together with a group that has strong attraction for the
solvent ,called the lyophilic group. This is known as amphipathic structure.
When a surface-active agent is dissolved in a solvent ,the presence of the
lyophobic group in the interior of the solvent may caused distortion in the
interior of the solvent liquid structure, increasing the free energy of the
Chapter Two
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Chapter Two
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Chapter Two
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reached ,in which region foam height reaches a maximum value or increases
slowly to a maximum value somewhat above the CMC. Thus, the CMC of a
surfactant is a good measure of its Efficiency as a foaming agent; the lower
the CMC, the more efficient the surfactant as a foamer. Those structural
factors that produce a lower critical micelle concentration for example,
increased length of the hydrophobic group-would therefore be expected to
increase the efficiency of the surfactant as a foaming agent (Rosen, 1989).
Those surfactants that are suitable for laboratory separation processes are
not necessarily appropriate for large-scale use, particularly environmental
applications, for example, they may be toxic, hazardous, and deleterious to
wildlife, chemically unstable or too expensive (Medina et al. 2005).
The types of ion separations that would be needed in a commercial
hydrometallurgical process differ from those typically encountered in the
laboratory. From an economic perspective, it will be essential that a metal
product can be removed from the foam with regeneration of the collector
(Doyle et al., 2003).
Focusing on surfactants that are likely to be acceptable, several anionic
surfactants with C12 alkyl chains have been used successfully for foam
flotation (Sreenivasarao and Doyle, 1997).
2.5 Frother
Frothers are heteropolar surface-active compounds containing a polar
group (OH, COOH, C=O, OSO2 and SO2 OH) and a hydrocarbon radical,
capable of adsorbing in the air-water interface. The frother molecules are
arranged at the airwater interface such that the hydrophilic or polar groups
are oriented into the water phase and the hydrophobic hydrocarbon chain in
the air phase. In fact, the frother creates conditions for froth formation. The
frother concentrates at the interface of water and air
Chapter Two
Literature Survey
bubbles forming an envelope around the bubbles, which prevents them from
colliding or touching (Bulatovic, 2007).
Frothers also lower the surface tension of the water due to heteropolar
nature of the reagent molecules Thus, the surface tension of a solution is an
indication of the activity of frother. Frothers that strongly lower the surface
tension produce more stable froths (Gupta et al., 2007).
The effect of frothers on bubble size has recently been extensively studied
(Cho and Laskowski, 2002; Laskowski et al., 2003; Grau et al., 2005; Gupta
et al., 2007; Melo et al., 2007; Nguyen et al., 2006; Comley et al., 2002). It
was found that the effect of frothers on bubble size results from their ability
to prevent bubble coalescence. As shown schematically in Fig. 2.3, with
increasing frother concentration, the degree of bubble coalescence decreases
and at a particular concentration (critical coalescence concentration, CCC),
the coalescence of the bubbles is completely prevented.
Figure 2.3 Schematic diagram of the effect of the frother concentration upon
bubble size in a flotation cell (Grau et al., 2005)
Chapter Two
Literature Survey
The CCC values are obtained by finding the intersection of the horizontal
asymptote to the bubble sizeconcentration curves at higher concentrations
with the sloped line approximating the curve at lower concentrations.
Further increase of the frother concentration above the CCC value does not
affect the bubble size (Grau et al., 2005).
Apart from the ability of frothers to form froth, they have other important
roles including (Bulatovic et al., 2007):
Creating finer bubbles, whereby the dispersion of air in the flotation cell
also improves.
Reducing coalescence of individual air bubbles.
Reducing the rate of bubble rise from the mixing zone to the froth zone.
Increasing the strength of the bubbles and stability of froth.
This may result from two interrelated actions: (a) improvement in air
dispersion and (b) deterioration in the coalescence of air bubbles in the pulp.
Both actions affect froth formation and bubble transport to the froth zone.
Molecules of the frother usually adsorb on air bubbles, thus increasing the
stability of the hydrated layer surrounding the bubble. The hydrophilic
groups of adsorbed frothers are directed to the liquid phase and actively
interact with molecules of water. This in fact leads to an increase in the
mechanical strength of the envelope surrounding the bubbles and prevents
destruction or collision with other bubbles (Bulatovic et al., 2007).
Experimental work carried out by Frumkin et al. (1947) demonstrated
that molecules of surface-active agents, which adsorb on the surface of
bubbles, are shifted to the bottom portion of the air bubble during their
upward movement in the liquid or pulp. This results in lowering the surface
tension in this region, creating difference in the surface tension between the
upper and lower region of the bubble. Along the surface of the air bubble, a
Chapter Two
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Chapter Two
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Chapter Two
Literature Survey
rate nor the type of impeller used can be related to floatability. Instead, it is
the bubble surface area flux Sb in the cell that is well correlated with the rate
of flotation.
Hardie et al.(1999) using column flotation for de-inking of recycled paper
showed that ink recovery was well correlated with bubble surface area flux.
Changunda et al. (2008) studies the effect of bubble size on the
flotation rate constant, they concluded that the flotation rate constant
increases approximately linearly with increasing particle size and follows an
inverse power relationship with the bubble size. This inverse power
relationship is due to the increased probability of collision for smaller
bubbles.The collisions between the hydrophobic particles and air bubbles
result in attachment to form bubble-mineral aggregates. Hydrophilic
particles do not attach to the air bubbles, remaining suspended in the water.
The air bubbles carry the attached particles to the surface of the cell forming
a froth zone.
Generally, both of these parameters ,gas flow rate and bubble size, have
been found to influence significantly the rate of the removal (Kinetic effect)
hence the retention time of the metals in the flotation cells and not
particularly the maximum removal using this effect, it has been found to be
possible the selective separation of different metals ions.
Chapter Two
Literature Survey
Matis et al. (1998) studied the effect of air flow rate on germanium ion
flotation by dispersed-air, involved the use of different fritted glasses in
the flotation cell. Changing the porosity of the bubble generator, different
bubbles size can be created, thus altering the total surface area of the
bubbles. Specially, if the mode of collection depends on the removed ion
and the surfactant ion meeting on the bubble surface, the residence time of
bubble must be sufficiently high to allow this proceed up to completion, this
sometimes can be over passed by finer bubbles. If it is not, some surfactant
floats wastefully and complete removal of the ion with stoichiometric
amount of surfactant becomes impossible.
Sulaymon and Mohammed (2010) studies the effect of hole diameters
(0.05 and 0.1 cm) of the gas distributer on the bubble diameters on
emulsified oil removal by flotation column.They concluded that the bubble
diameter increase since the increase in hole diameter resulted in a decrease
in bubble rise velocity for a given gas flow rate. New correlations of bubble
diameter were derived:
=0.023[ ]0.053 [ ] 0.08 [ ] 0.12 (2-1)
Where:
Chapter Two
Literature Survey
Recent studies have shown that changes in concentrate grade and recovery
can be linked to changes in froth stability as operating parameters are varied
(Banford et al., 1998; Ventura-Medina and Cilliers, 2002; Barbian et al.,
2005; Hadler et al., 2009). In these studies, froth stability has been
quantified using air recovery.
A stable foam (or more correctly a persistent foam, since foams are not
thermodynamically stable due to their higher high interfacial free energy) is
produced when the rupture of the lamellae is prevented even after most of
the liquid has drained out of it. The stability of foam can be quantified as the
time that elapses between its formation and its collapse. In general, the
longer the collapsing time, the more stable the foam (Pugh et al., 1996).
One of the simplest methods for determining the stability of foam is by
measuring the height of a foam column as a function of time (Wilson, 1996).
There are three basic mechanisms involved in foam collapse: drainage,
film rupture and bubble coalescence .Several forces act on the thin films in
the foam structures and causes either stabilising or destabilising effects.
Drainage of liquid from the foam lamellae due to gravity is a
destabilising effect, which results in film thinning. At a critical thickness of
50-100 Ao the film will rupture due to attractive Vander Waals Forces
leading to coalescence of two bubbles(Wilson, 1989).
The dependence of foam stability on surfactant depends upon a number
of factors, including the chemical structure of the surfactants, surfactant
concentration, etc. Tamura et al. (1998) suggested in their recent study that
surfactant structure plays a role in the drainage of foam films. For a nonionic
surfactant, increases the hydrocarbon chain length results in an increase
intermolecular hydrophobic interaction in the adsorbed surfactant and thus
an increase in the foam films lifetime. By contrast, increase the relative size
Chapter Two
Literature Survey
Chapter Two
Literature Survey
Conditioning
Solution
Foam
Ion flotation
Metal product
Figure 2.4 flow chart showing how ion flotation with dodecylsulfate and
electrolytic metal recovery could be used to remove residual metal ions from
a process effluent (Doyle et al., 2003)
2.9 Modifiers
This class of reagents covers all chemicals whose principal function is
neither collecting nor frothing. These may be further divided into
depressants, activators and pH regulators. A depressant is any chemical
which inhibits or prevents the adsorption of a collector by a mineral particle
and thereby prevents its flotation. An activator prepares the mineral surface
Chapter Two
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Chapter Two
Literature Survey
( ) =k Cn (2-3)
This is the basic rate equation, in which the value of n denotes the order of
the equation and k is the flotation rate constant. Integration of Eq. (2-3) with
n = 1 (first order) gives:
Chapter Two
Literature Survey
C = Coe-kt (2-4)
Where Co= the concentration of valuable material at zero time, and C = the
concentration of valuable material remaining at time t. Taking the ln of Eq.
(2-4):
ln ( ) = -kt (2-5)
And if the experimental values of ln (C/Co) are plotted against t, the graph
should be a straight line of slope k if n = 1(Gupta et al., 2006).
The rate constant, k, within this equation conveys how rapidly one species
floats. A high rate constant indicates that certain species floats quickly while
a low rate constant indicates slow flotation.
Chapter Two
Literature Survey
Chapter Two
Literature Survey
and sodium hydroxide was a more effective neutralizing agent than was
sodium carbonate (soda ash).
Matis et al., 1991 examined the removal of two metal ions copper and
chromates by applying two flotation techniques: precipitate and adsorbing
colloid flotation. They deduced the conclusions that; collector (SDS) and
frother (ethanol) concentrations had no significant effect on copper removal,
collector concentration had no effect for chromium removal and comparison
of the three flotation techniques (precipitate, sorptive and adsorbing colloid
flotation),in a hybrid configuration ,revealed that precipitate flotation had the
better influence on membrane performance.
Zouboulis et al.,1995 investigated the recovery of silver from dilute
aqueous solutions containing complexion agent by ion flotation .In this
study ,the objective was to establish the optimum conditions such as pH,
surfactant ,silver and thiosulphate concentrations in order to apply the
method to synthetic solutions. Experiments were performed using cationic
surfactant dodecyl amine (DA), as frother ethanol .High recoveries of silver
from aqueous solutions containing thiosulphates and optimum conditions for
the recovery of silver were obtained.
Experimental investigations on the removal of Cd (II) from aqueous
solution were carried out using a foam separation technique with sodium
lauryl sulfate and sodium laurate by Choi et al., 1998.The effects of pH,
surfactant, and foreign ions on the efficiency of Cd (II) removal rate
discussed. Foam flotation with sodium laurate gave better removal
efficiency than with sodium lauryl sulfate
Charewicz et al., 1999 examined the batch flotation of zinc (II) and silver
(I) ions from dilute aqueous solutions with sodium dodecyl sulphate and
ammonium tetradecylsulfonate as anionic surfactants and with cetylpy-
ridinium chloride as a cationic surfactant. Also, they studied the effect
Chapter Two
Literature Survey
of inorganic ligands (thiosulphates, thiocyanates) on the selectivity of ion
flotation of Zn (II) and Ag (I) ions. They found that Zn (II) and Ag (I) could
be separated from diluted aqueous solutions with anionic surfactants since
Zn+2 cations exhibited a much higher affinity for a surfactant than did Ag+
cations. The separation of metal ions was also possible when solution
contains thiosulphate or thiocyanate ligands.
The removal of Cd (II) using SDS as a collector was studied by Scorzelli
etal.,1999.They also studied in the effect of frothers and the surface tension
of the initial solutions. Iso-propanol and methylisobutylcarbinol (MIBC)
were used as frothers. Characterization of the sublate by scanning electron
microscopy (SEM) were also examined to understand what occurs during
ion flotation. Surface tension data and SEM results showed the reduction in
floatability which was related to the adsorption of SDS at interface liquid-
gas. The best recovery was obtained as 88.2% in the presence of SDS.
A thermodynamic approach was investigated to model the removal of
cupric ion from (sodium dodecylsulphate)SDS-Cu,(sodium tetradecyl
sulphate)STS-Cu and (sodium hexadecylsulphate)SHS-Cu ion flotation
systems by liu et al.,2001.They obtained surface tension data a wide
concentration range of each alkylsulphate-copper solution. They used the
data to fit analytical regression equation and differentiated to generate an
expression for the metal ion adsorption densities. They demonstrated that the
more active collectors gave faster metal removal kinetics and were capable
of attaining much lower steady-state copper concentrations and they built up
a model for the copper removal kinetics.
Doyle et al., 2003 observed the fundamental characteristics for ion
flotation in the context for their implications for commercial applications.
These characteristics included the kinetics for metal ion removal, the ability
to recover metal values from the foam product, the ability to separate ions
Chapter Two
Literature Survey
selectively from mixed solutions and a comparison of the performance of ion
flotation with other separation methods.
Doyle et al., 2003 reported that the effect of a neutral chelating ligands,
triethylenetetraamine (Trien) on the ability to separate copper (II) and
calcium (II) ions and compared the ion flotation behavior of Cu+2 and Ni+2
ions with the behavior of Cu-Trien and Ni-Trien complexes .In experiments,
SDS was used as the collector .They concluded that copper was removed
preferentially, whereas in the absence of Trien, the calcium was removed.
Trien was shown markedly increase the removal rates of Cu+2, Ni+2 during
ion flotation with SDS and lower the steady state concentration reached.
Surface tension measurements confirmed that Trien enhanced the surface
activity and adsorption density for SDS Cu (II) and SDS-Ni (II) solutions.
A study concerning the kinetics of Cu+2 ion separating by precipitate
flotation using alkyl amine type (laurylamine) and alkylammonium salt
(lauryltrimethylammonium chloride)as cationic collectors and alkylsulphate
and alkylcarboxilic type (sodium laurylsulphate and sodium oleate) as
anionic collectors was presented by Stoica et al. ,2003.Obtained data were
used to verify the classical the first order model and there other first order
models, adjusted to the classical model.They found Cu(II)hydroxide species
separation using precipitate flotation followed an overall first order kinetic.
Zouboulis et al., 2003 investigated the removal of Zinc and chromium
ions from aqueous solutions by application of a two-stage separation
process. The first part consisted of the metal ions sorption onto an
appropriate sorbent material and successive flotation followed as the second
part. The biologically produced surface active agents Surfactin-105
and Lichenysin-A were as alternative collectors for flotation methods. The
conclusion was drawn from experimental data; biosurfactants effectively
removed sorbent material and presented. Both biosurfactants removed
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Chapter Three
Experimental Work and Procedure
3.1.2 Gas
Air was the type of gas used in the present study (compressed at 1 bar up
to 7 bars) was supplied by a compressor.
Chapter Three
Experimental Work and Procedure
Then the solution was placed in the flotation column. Foam samples were
taken at preset time intervals as 5, 10, 15, 20, 25, 30, 35 and 40 minutes. A
port 0.45 m above the base was used for periodic sampling. About 3ml of
solution was drained from the port before withdrawing each sample; samples
were withdrawn slowly, to minimize entrainment of air bubbles. Between
experiments, the column was cleaned using HNO3, and then rinsed three
times with double distilled water. The apparatus used in the experiment
were:
pH-meter (WTW,Sr.Nr:08490207)
Atomic Absorption Spectrometry (AAS) (Perkin Elmer, Sr.Nr:1159A)
Chapter Three
Experimental Work and Procedure
6 cm
30cm
Foam
15cm Flotation Column
15cm
15cm
15cm Rotameter Pressure Gauges
15cm
15cm Filter Air
Distributor
Needle Valve
Chapter Four
RESULTS AND DISCUSSION
4.1 Effect of pH
Several works related to the foam separation techniques point out that pH
plays an important role in flotation. Depending on pH, different interfacial
properties and reaction routes may be found (Matis and Mavros, 1991).
The effect of pH on the recovery of copper by bubble column is shown in
Fig.4.1by plotting the removal ratios versus time at various pH values .As
shown in this figure the removal ratios decreases suddenly after
approximately ten minute from the beginning of the run ,then ,these ratios
began to decrease slowly with time. It was found that the highest removal
achieved when the pH of the solution was 10.
This result was similar to Polat and Erdogan (2007).They suggested that
the charge of copper ion was positive Cu+2, CuOH+ at pH below 10 whereas
they are negatively charged Cu(OH)-3 and Cu(OH)4-2 at pH values greater
than 10. At and around pH 10, precipitation of neutral Cu(OH)2 takes place.
The formation of the precipitation of Cu(OH)2 can explain the higher
recovery for pH values at and around 10.
The removal rate constant at various pH was found by plotting ln (Co/C)
against time according to equation (2.5).The rate constant obtained at
various pH values were plotted in fig.4.2 and their values were tabulated in
Table 4.1.It can be seen that the higher rate constant (k=8.7 10-2) is
obtained at pH=10 .
Chapter Four
Results and Discussion
pH=4,SDS
1 pH=6,SDS
0.9 pH=8,SDS
0.8 pH=10,SDS
0.7 pH=12,SDS
0.6
C/Co
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
Chapter Four
Results and Discussion
pH k102 (min-1)
4 0.6
6 1.2
8 4.0
10 8.7
12 2.4
Chapter Four
Results and Discussion
1 pH=4,SDS
pH=6,SDS
0.9
pH=8,SDS
0.8
pH=10,SDS
0.7
pH=12,SDS
0.6 pH=10,HTAB
C/Co
Chapter Four
Results and Discussion
Chapter Four
Results and Discussion
kinetic model proposed by Gupta et al. (2006), although the deviation is not
too significant.
1 SDS=125 mg/l
0.9 SDS=75 mg/l
0.8 SDS=25 mg/l
0.7
0.6
0.5
C/Co
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time (min)
1
SDS=75mg/l
0.9
0.8 SDS=225mg/l
0.7 SDS=350mg/l
0.6
0.5
C/Co
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
Chapter Four
Results and Discussion
0
-0.5
125 mg/l
-1
75 mg/l
-1.5
25 mg/l
-2
ln(C/Co)
-2.5
-3
-3.5
-4
-4.5
-5
0 5 10 15 20 25 30 35 40
Time(min)
Co(mg/l) k102(min-1) n
25 7.6 1.080
75 8.7 1.065
Chapter Four
Results and Discussion
4.4 Effect of initial copper concentration
The removal rate of copper at various initial copper concentration is
shown in Fig.4.4 and Fig.4.5 by plotting (C/C0) rate versus time at pH=10
and pH=4 respectively. From these figures, it was found that copper
concentration has a much greater effect on removal rate at pH=4 than at
pH=10.
Fig.4.4 shows the effect of increasing copper concentration at pH=10
where the precipitate take place. It can be seen that there is no significant
difference in removal rate with increasing copper concentration from
100mg/l to 200mg/l. However at low copper concentration (25mg/l) the
removal rate decreased because of large surfactant: copper ion ratio which
cause competition, for bubble surface, between the metalcollector product
and free collector ions (Shakir et al., 2010).
Fig.4.5 shows the effect of increasing copper concentration at pH=4.
It can be seen that decreasing copper concentration leads to increase
removal rate. This result was similar to Zouboulis et al. (1990).They
suggested that an increased metal ion concentration increased collector
required for same percent removal.
The removal of copper ions at pH=10 where copper hydroxide
precipitation take place was more efficient, rapid and virtually complete
within a relatively short time than the removal of copper ions at pH=4.It was
much less sensitive to the difference in copper concentration than removal at
pH=4 and it becomes clear that in each system to be separated, certain
optimum ratio of reagents exists.
The removal rate constants at various copper concentrations were
found and their values were tabulated in Table 4.2.
Chapter Four
Results and Discussion
1
0.9 cu=25 mg/l
Figure 4.7 Effect of copper concentration on the removal rate (pH=10; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm).
1
0.9
0.8
0.7
0.6
C/C0
0.5
0.4
Cu=25mg/l
0.3
Cu=50mg/l
0.2
Cu=100mg/l
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
Figure 4.8 Effect of copper concentration on the removal rate (pH=4; SDS
=75mg/l; Q =250 ml/min; Ethanol=1%,do=1mm).
Chapter Four
Results and Discussion
Co(mg/l) k102(min-1)
25 4.7
100 8.7
200 7.0
1
0.9 Q=100 ml/min
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
Figure 4.9 Effect of gas flow rate on the removal rate of copper (pH=4;
Co=25 mg/l; SDS=350 mg/l; ethanol=1%,do=1mm).
1
0.9
0.8 Q=100 ml/min
0.7
Q=250 ml/min
0.6
Q=500 ml/min
0.5
C/Co
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
Figure 4.10 Effect of gas flow rate on the removal rate of copper (pH=10;
Co=100 mg / l; SDS=75 mg/l; ethanol=1%,do=1mm).
Chapter Four
Results and Discussion
The removal rate constants at various gas flow rate were tabulated in
Table 4.4.It can be seen that the rate constant increased with increasing gas
flow rate.
Q(ml/min) k102(min-1)
100 3.0
250 8.7
500 4.6
1
0.9
d=1mm
0.8
d=o.5 mm
0.7
0.6
0.5
C/Co
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time (min)
Figure 4.11 Effect of hole diameter of the gas distributor on the removal rate
of copper(pH=4;Co=25mg/l;SDS=350mg/l; Q=250ml/min; ethanol = 1 % ).
Chapter Four
Results and Discussion
without ethanol
1
0.9 ethanol=1%
0.8 ethanol=2%
0.7
0.6
C/Co
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
1
without ethanol
0.9
ethanol=1%
0.8
0.7 ethanol=2%
0.6
C/Co
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
1 8.7
2 5.2
Chapter Four
Results and Discussion
1
0.9 without NaCL
0.8 NaCL=25mg/l
0.7 NaCL=50mg/l
0.6
C/C0
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
Figure 4.14 Effect of NaCl concentration on the removal rate of copper
(pH=4; Co=25 mg/l; SDS=350 mg/l; Q=500 ml/min; ethanol = 1% ,
do=1mm).
Chapter Four
Results and Discussion
1
without NaCL
0.9
NaCL=25 mg/l
0.8
NaCL=50 mg/l
0.7
0.6
C/Co
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35 40
Time(min)
50 4.0
Chapter Five
CONCLUSIONS AND
RECOMMENDATIONS
5.1 Conclusions
1. Higher percentage of copper ions removal were achieved at low time (40
min) about 98% for pH=10,Co=100 mg/l, SDS=75 mg/ l , ethanol =
1%,Q=250 ml/min, do=1mm, and about 80% for pH=4,Co=25 mg/l,
SDS=350 mg/l, Q=500 ml/min, ethanol=1%,do=0.5mm.
2. The anionic surfactant (SDS) was found to be more efficient than
cationic surfactant. At pH lower than 10, no significant removal rate was
obtained using HTAB. Maximum removal rate 98% was achieved at pH
= 10 using SDS while maximum removal rate 76% was obtained using
HTAB at pH=12.
3. The best removal of copper ions was achieved at pH= 10.0 and the effect
of various variables at this pH was studied.
a. Increasing the initial copper concentration from 100 to 200 mg/l no
change in the removal rate which was 98% after 40 min of flotation
time; however, decreasing the copper concentration to 25 mg/l
decreased copper removal to 94% due to high surfactant to metal
ratio.
b. Collector concentration had very little affected on the removal rate in
the range 25 to 75 mg/l; however, further increasing of SDS
concentration to 125 mg/l decreased the removal rate to 96%.
c. Added ethanol of 1% increased the removal rate from 91% to 98%;
Chapter Five
Conclusions and Recommendations
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APPENDIX
Table 5 Residual Copper Concentration at Different pH, Co = 100 mg/l;
SDS=75mg/l, HTAB=75mg/l, Q=250ml/min, Ethanol=1, do=1mm.
Appendix
C/Co
Time (min) SDS HTAB
C/Co
Time(min) 25 mg/l 50 mg/l 100 mg/l
5 0.820 0.868 0.940
10 0.770 0.827 0.858
15 0.699 0.776 0.816
20 0.664 0.739 0.805
25 0.641 0.715 0.796
30 0.624 0.707 0.787
35 0.619 0.694 0.775
40 0.617 0.694 0.761
Appendix
C/Co
Time (min) 25 mg/l 75 mg/l 125 mg/l
5 0.104 0.152 0.212
10 0.122 0.104 0.177
15 0.108 0.069 0.087
20 0.044 0.037 0.083
25 0.039 0.031 0.080
30 0.033 0.025 0.075
35 0.025 0.017 0.049
40 0.025 0.017 0.039
C/Co
Time (min) 75 mg/l 225 mg/l 350 mg/l
5 0.820 0.772 0.725
10 0.770 0.690 0.628
15 0.699 0.613 0.520
20 0.664 0.557 0.467
25 0.641 0.499 0.383
30 0.624 0.458 0.329
35 0.619 0.436 0.320
40 0.617 0.430 0.317
Appendix
Table 10 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=10,
Co =100 mg/l, SDS=75 mg/l, Ethanol=1%, do=1mm.
C/Co
Time (min) 100 ml/min 250 ml/min 500 ml/min
5 0.300 0.152 0.245
10 0.270 0.104 0.150
15 0.240 0.069 0.104
20 0.220 0.037 0.100
25 0.210 0.031 0.097
30 0.185 0.025 0.092
35 0.183 0.017 0.085
40 0.182 0.017 0.085
Table 11 Effect of Gas Flow Rate on the Removal Rate of Copper, pH=4, Co
=25 mg/l, SDS=350 mg/l, Ethanol=1%, do=1mm.
C/Co
Time (min) 100 ml/min 250 ml/min 500 ml/min
5 0.862 0.725 0.655
10 0.748 0.628 0.503
15 0.635 0.520 0.433
20 0.588 0.467 0.378
25 0.525 0.383 0.301
30 0.477 0.329 0.251
35 0.449 0.320 0.210
40 0.448 0.317 0.199
Appendix
C/Co
Time (min) (Zero) (1%) (2%)
5 0.199 0.152 0.155
10 0.119 0.104 0.080
15 0.110 0.069 0.072
20 0.099 0.037 0.068
25 0.093 0.031 0.057
30 0.091 0.025 0.056
35 0.090 0.017 0.055
40 0.090 0.017 0.055
C/Co
Time (min) (Zero) (1%) (2%)
5 0.790 0.725 0.827
10 0.688 0.628 0.716
15 0.590 0.520 0.653
20 0.497 0.467 0.579
25 0.452 0.383 0.527
30 0.422 0.329 0.500
35 0.406 0.320 0.475
40 0.405 0.317 0.470
Appendix
C/Co
Time (min) Zero 25 mg/l 50 mg/l
5 0.152 0.270 0.350
10 0.104 0.200 0.250
15 0.069 0.155 0.210
20 0.037 0.130 0.200
25 0.031 0.125 0.195
30 0.025 0.124 0.198
35 0.017 0.122 0.194
40 0.017 0.121 0.191
C/Co
Time (min) Zero 25 mg/l 50 mg/l
5 0.655 0.750 0.844
10 0.503 0.610 0.690
15 0.433 0.510 0.597
20 0.378 0.498 0.576
25 0.301 0.476 0.568
30 0.251 0.450 0.555
35 0.210 0.420 0.552
40 0.199 0.415 0.550
Appendix
Table 16 Effect of hole diameter of the gas distributor on the removal rate of
copper, pH=4, Co=25 mg/l, SDS=350 mg/l, Q=250 ml/min, Ethanol=1%.
C/Co
Time (min) do=0.5mm do=1mm
5 0.698 0.725
10 0.545 0.628
15 0.449 0.520
20 0.378 0.467
25 0.312 0.383
30 0.279 0.329
35 0.259 0.320
40 0.249 0.317