Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Kenneth J. Ives
Professor of Public Health Engineering
Department of Civil and Municipal Engineering
University College, London, U.K.
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Distributors for all other countries: Kluwer Academic Publishers Group, Distribution
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Acknowledgement VI
K.J. Ives
Introduction 1
J.A. Kitchener
The Froth Flotation Process: Past,
Present and Future - In Brief 3
G.J. Jameson
Physics and Hydrodynamics of Bubbles 53
P.L. de Bruyn
Some Aspects of the Physical Chemistry
of Solid/Water Interfaces 111
G.J. Jameson
Experimental Techniques in Flotation 193
H.L. Shergold
Flotation in Mineral Processing 229
G. Barbery
Engineering Aspects of Flotation in the
Minerals Industry: Flotation Machines,
Circuits and their Simulation 289
T. Zabel
Flotation in Water Treatment 349
H.H. Hahn
Wastewater Treatment 379
Index 415
Appendix 425
List of those attending the NATO Advanced Study
Institute of Christ's College, Cambridge (UK)
5-16 July, 1982
VI
ACKNOWLEDGEMENT
This book would not have been possible without the support
and cooperation of the Division of Scientific Affairs, NATO,
Brussels, and the particular help given by its Director Dr. C.
Sinclair, and his staff, which is gratefully acknowledged.
Kenneth J. Ives
1
INTRODUCTION
K.J.Ives
J.A.Kitchener
FOREWORD
HOW IT BEGAN
* copyright J.A.Kitchener
4
2. When sulphide minerals are agitated with oil and water they
are preferentially wetted by the oil, in contrast to the
common gangue minerals (oxides, silicates, carbonates etc.)
which are hydrophilic rather than oleophilic (Bradford,
1860).
10. The time was now ripe for the key invention. According to
T.A. Rickard [lcI. the efforts of the Minerals Separation
Ltd. research team in London were rewarded when "suddenly
they happened upon the particular combination essential to
the froth flotation process". The simplest and cheapest way
of floating sulphide minerals is to vigorously agitate the
finely-divided ore in water with entrained air. together
with only a very little oil ("a fraction of 1% of the weight
of the ore") for a period of 1 to 10 minutes. This is the
crux of the classic British Patent No.7803 (Sulman.Picard
and Ballot. 1905). The use of a very small proportion of oil
7
THE FOUNDATIONS
CLASSIC DEVELOPMENTS
The problem with the mixed sulphide ores was that pyrite (FeSZ)
also 'floated, especially in acid conditions. Myers (1915)
recalled that they had never been troubled with pyrite when
floating a naturally alkaline ore. Sure enough, raising the pH
proved effective in preventing pyrite floating ("depressing"
it). For no obvious reason lime, Ca(OH)2, was found to be more
effective than NaOH - so i t wasn't just the pH that caused
depression.
CHEMICAL REAGENTS
HOPEFUL IDEAS
NON-MINERAL FLOTATION
Since the second World War, there has been a flood of articles
describing the use of flotation for purifying effluents. most
of them read as though the authors had just invented the
process, whereas in truth many applications had been patented
(if not actually used) before 1945. A scan of the Chemical
Abstracts for the period 1917-1946 under "Flotation" reveals
applications to a wide range of materials, including the
following:-
RESEARCHING FLOTATION
MOTOR
....
,
./'
.
r /'~~~'
c. )
fI
••. 66 c)
'.
Ci ..
feed
slurr~~~.~.'~.~I~··~.1."~IE~~DlIIIIIICliiaialli
air -
- ---
- -
recycle water
Fig.2.Schematic diagram of a dissolved air flotation
plant
A. Physical aspects
1. What makes some solids readily floatable, others
poorly floatable, and some not at all?
B. Chemical aspects
(b) With the glass beads, which had the same surface
properties as the treated quartz, the flotation rate
was appreciably lower than with quartz particles. The
difference can be ascribed, with fair confidence, to
the effect of angularity (roughness) on the rupture of
wetting films.
I. Elemental minerals
II. Sulphides
III. Oxides (simple,single or dual cations)
IV. Silicates and alumino-silicates
V. Salt-type minerals
sulphur), S °z
x y
('sulphoxides', such as S202: thiosulphite;
3
SH062- ,tetrathionate)and finally sulphate S042- .The so called
"Pourbaix diagram" (E - pH) shows what products are possible
or thermodynamically s~able, but gives no information about the
mechanism or rate at which the reactions occur. In dry air the
oxidation is very slow, but in water it proceeds by a mechanism
similar to the corrosion of metals; for the sulphide minerals
are electrical semi-conductors, and "local cells" are found
between spots on the surface which are relatively anionic and
others which are relatively cathodic. A scan over the surface
of a sulphide mineral with a micro-electrode reveals these
heterogeneities of electrochemical potential.
Oxides are not soluble as such in water because the Oz- ion
reacts to form 2 OH • The same reaction occurs on the surface
of all oxides listed, but generally only to the extent of a
monolayer. In principle, oxides "ought to" change into
hydroxides; periclase, MgO, does change extremely slowly to
brucite, Mg (OH)z; but corundum, AlZ03' seems not to get beyond
a monolayer, although gibbsite, Al(OH)3, is the thermo-
dynamically stable phase in water.
-AIOH + HCl ~
+ -
-AIOllzCl, and
-AIOH + NaOH ~ -AIO Na + HzO
The OH group behaves as a weak acid or a weak base, the actual
dissociation constants depending on the metal cation. The
insoluble oxides can therefore be titrated electrometrically.
v. Salt-type minerals
ea 2+ F (Ce,La,Th)(PO )
2 It
iodyrite, AgI, which, in its pure synthetic form, has been much
studied by colloid chemists as a model. Its solubility product
is about 10- 16 (mol R.-1)~ wh~ch sho~s that_ in pure water i t
would dissolve until [Ag ]=[ I ] = 10 Bmol i 1. (Neither ion is
greatly hydrolyzed.) Yet electrophoresis experiments show that
AgI adopts a negative zeta-potential in pure water. To bring it
to its p.z.c. one must add a slight excess of some soluble Ag-
salt; the concentration required is only about 10- 6 , which
corresponds, of course, to [1-] = 10- 1°. In the region of the
p. z. c. the potential approximates to that given by the Nernst
equation, and the lattice ions are said+ to be _"potential-
determining", whereas other ions such as Na and NO 3, which may
happen to occur in a pulp, have little influence. It is correct
to regard both the lattice ions as being "specifically
adsorbed" by the solid, and therefore competing to fix the
surface potential. On this vief' 1- ions are adsorbed by AgI
10 4 times more strongly than Ag ions.
II. Sulphides
III. Oxides
V. Salt-type minerals
Organic depressants
Improvements
When any technical process has been in used for many years and
has not had the benefit of renewed, adequately-funded, R. and
D., there is a very good chance that its efficiency could be
improved. The following case of an old-fashioned mineral
treatment process - lime-burning - will illustrate the point.
Extensions
REFERENCES
G.J.Jameson
INTRODUCTION
100
Spherical
40
III
.......
E
u
~ 20
>-
I-
......
U
0
....I
lJ.J
10
>
lJ.J
V')
......
0::::
lJ.J
....I 4
CXl
CXl
:::>
CXl
2
1 4 10 40
BUBBLE DIAMETER, mm
Figure 1. The terminal velocity of air bubbles in water at
20 0 C, after Clift et a1. [3]
The other effect that is seen with these bubbles. is that they
are no longer spherical, but resemble flattened spheroids or
ellipsoids. Small bubbles are held in the spherical form by
surface tension, whose effect diminishes inversely as the
56
(1)
(2)
CD = 24/Re. (4)
(5)
u = 11>.8!!..2 [ l:!:.K ] ,
3lJ 2+3K
a result known as the Hadamard -Rybczynski equation.
When K~, the result for a solid sphere, eq.(2), is recovered.
For a bubble, K+O and the equation predicts that the rise
velocity should be 1.5 times that of solid sphere of the same
density.
(6)
c =~ [ 2+3K ].
D Re l+K
It is interesting to note that in a true Stokes regime with
Re+O, surface tension is unnecessary as a means of maintaining
sphericity. As Batchelor [8] points out, the pressure around
the surface due to the viscous stresses varies in exactly the
same way with angular position as the hydrostatic pressure, so
that at every point, it is possible to obtain exact equality
without the need to invoke surface tension as the balancing
component.
c = ~ [1 - 2.211 ] (7)
D Re ----r-.
2
Re
This equation should be expected to hold for "large" Reynolds
numbers, whenever the bubble is spherical. Harper [1] suggests
Re = 50 as the lower limit, corresponding to an air bubble of
diameter 0.5mm, and experimental evidence is that bubbles in
water remain spherical for diameters up to about 1mm. As will
be seen later, it appears that between 0.6 and 1mm diameters,
eq. (7), overpredicts the rise velocity. Beyond 1mm the rise
velocities predicted continue to increase with increasing
diameter, contrary to observation.
ELLIPSOIDAL BUBBLES
60
VI 40
'-
E
u
- --
ft 30
>-
I-
......
U
0
-l
l.LJ
:::- 20
l.LJ
V)
......
~
10
0.4 1 2 4 5
BUBBLE DIAMETER, mm
SPHERICAL-CAPPED BUBBLES
2
P + !PV 8 + pgy = constant (8)
g R(l-cos8). (9)
" ""
" ""
"
" ""
""
o
Figure 3. Flow around a spherical-capped bubble rising in a
liquid.
62
3
Va = 2" U sin a (10)
2 .1
U ="3 (gR) 2 (1l)
U 0.792 (g Vl/3)!
These results are valid for large bubbles provided the bubble
Reynolds number is greater than 40 [3]
When we move away from the air-water system, we move into the
area of generalised variables. Apart from the Reynolds number
Re and the drag coefficient CD' the relavent dimensionless
groups are:
y pu 2d/a (14)
F U2/gd (1S)
Liquid M
W (4 M Re lf /3 C ) 1/3 (17)
D
F 4/3 ~, (18)
3
B2 =-W
E ~, (19)
4
a
p
a = II = RTr (20)
14
//
A// B
,'1
12 ,'1
,/ o
,'/ o
10 '
VI
...... ,'/
//
E
u
8
E/ 1/
~
>-
t-
/1
........
U
a I
/ / I.
...J
w 6
:>
w
U')
........
I It'
0::: / /. 00
W 4
...J
co
co
::::>
co
2
1.0
0.8 SOLID
SPHERE
0.6
Co
0.4
"INVISCID"
SPHERE
MOOR~I]
0.2
...,,-
J,
0.1
60 80 100 200 400 600 800
Re
Figure 5. Experimental results of Detwiler and Blanchard [14]
showing the effect of bubble age on the drag
coefficient. Each straight line represents one bubble
size (950,1010,1080,1270 and 1310pm respectively),
with the rise velocity determined at various times
after formation. The newly-formed agree closely with
Moore's theory [11] but with increasing age they
approach solid-sphere behaviour.
68
The idea that assorption phenomena and flotation are linked was
developed in Russia by Derjaguin and Dukhin, the broad outlines
being published in 1961. [15] They suggested that a bubble
could be considered to be surrounded by three zones. Close to
the surface of the bubble is a region in which any particle
which finds itself will be under the influence of the "surface"
forces - the London - van der Waals and double-layer attraction
or repulsion. Further away, there is a region where "diffusio-
phoretic" forces are important, where the conetration gradients
of ionic species and hence the gradients of electrical
potential, may interact with the small charged solid particles
approaching the surface of the bubble. Finally, outside the
range of the double-layer and the mass transfer boundary layer,
the interaction between particle and bubble is dominated by the
prosaic viscous and intertial effects of conventional fluid
mechanics.
nd a = nd 3 g~p/6
o
or d = (6d a/g~p)1/3. (21)
o
This simple equation is not particularly accurate; predicted
bubble volumes may be in error by a factor of up to 2. This is
not surprising because the bubbles do not usually detach as
spheres, but have elongated necks. Corrections can be made
using the factor of Harkins and Brown, [25] well known for its
applicability to pendant drops.
(23)
ds
pVg 611}.lr dt ' (24)
Flotation cells are not the only equipment in which bubbles are
generated with rotating impellers. Such devices are widely used
in biochemical engineering to provide oxygen for the growth of
micro-organisms. For this reason there have been several
detailed investigations into bubble generation which show that
other mechanisms are at work in addition to the simple
ventilated cavities seen by Grainger-Allen.
Van's Riet and Smith [28-31] have shown that, at least at low
air rates, trailing vortices develop at the corners of the
turbine blades, and air is drawn into the centre of the vortex;
,,
(b)
./
./
(a) (b)
NOTATION
Dimensionless groups
REFERENCES
INTRODUCTION
a.
A w
b.
A
CD
81 / \
/ \
/ \
w
I \
1
/
\\
o - 0
SA SW (1)
cos 9
o
WA
(2)
o - 0
cos a SA
o
SW
- --
0 r
T (3)
WA WA
If only Van der Waals dispersion forces act between Sand L, i.e.
if polar contributrions are absent in at least one of the phases,
the result is:
(6)
do
i r (i SA,SW,WA) (8)
dll i
d(o - ° r - r
SA SW SA SW
do r
WA WA (10)
o
aWA (mNm-I )
-40
(1) 0WA cos e is a linear function of 0WA over the entire range
of surfactant concentration from zero up to the limiting
concentration [33-36]
(12)
+40
80
o
a (mNm-I)
-40
aWAcos8
(mNm- I )
+40
-40
aWAcos8
(mNm- I )
+40
o
aWA(mNm-I )
Nonequilibrium adsorptions
not too dissimilar from that for the platinum system, so the
proximity of the nonequilibrium points to the equilibrium line
strongly suggests that the dynamic surface tension O'UA alone
determines the contact angle in this case. This sugges-Uon is
less surprising when it is considered that in the circumstances
of these experiments the adsorption rSU is probably close to its
equilibrium value, and that the interfacial tension O'SA is
practically constant in the ascending part of the platinum curve,
where Eq(ll) is obeyed. Hence the dynamic contact angle is
probably determined by the kinetics of adsorption at the
air/water surface alone.
£
6P = r (14)
Recent years have seen such attention paid to the mechanism and
the kinetics of film thinning and rupture, which is regarded by
some [2,54-55] as the most important stage in flotation.
Mechanisms of film breaking have been identified for both the
early stages of a film's life, at relatively large thicknesses
where the spheres of influence of the approaching interfaces do
not yet overlap, and for the later stages where the film has
thinned down to dimensions where interaction forces across it
determine the behaviour. These two stages merit separate
consideration.
(15)
"
LOW
SOLID
Figure 6. Response of liquid film to transport of compound which
lowers the surface tension
------ direction of transport
direction of Marangoni flow
(16)
-do~lnr
tE = ---::;~ (17)
f l+th dc /dr
Gibbs elasticity has long been suspected of being an important
parameter in stabilising thin films and foams [70]. The relation-
ship between stability and Gibbs is an indirect one. however.
96
a.
1
0.1
0.01
0.1 1 10 100
h/ho
E (mNm- I ) b.
30
20
10
o~------------~-------------L--------~
0.05 0.10
C(mol m- 3)
Figure. 7. a) Thickness dependence of Gibbs elasticity according
to Eqn(17). t E in units E = - da/dlnr; h in units
h = 2dr/dc 0
b) C8ncentration dependence of Gibbs elas ticity;
numerical examples calculated for Langmuir
adsorption, from data of ref.69.
97
Both the earliest [63] and the latest [69] theories hold that
Gibbs elasticity can impart stability to a film only if it
increases when the thickness of the film decreases: it is the
thinnest part of a film which is in most danger of rupture and in
need of resitance against further deformation. In conditions
where Eq(17) applies, i.e. in films undisturbed by processes
other than re-equilibration of surfactant in the film, it is
clear that at given concentration Gibbs elasticity is always
higher in the thinner parts, thus tending to stabilise the film:
see Fig 7a. However, in a draining film with mobile surfaces,
continued surface expansion means that both the surface and the
film liquid will suffer depletion of surfactant, i.e. the
concentration c will decrease. A typical example of the
concentration dependence of E is given in Fig. 7b. Numerical
values here were calculated assuming a specific relationship
between o,r and c, but the occurrence of a maximum in the curves
is general [66]. It is only on the left-hand side of the maximum
that surfactant depletion in a thinning film can lead to a
decrease in E, and hence to destabilisation of the film, as
argued in a recent review (69). In this region, i.e. at fairly
low concentrations, films are liable to rapid disproportionation
into thinner and thicker parts, as the thinner parts offer less
and less resistance to further thinning.
(18)
~ '> 0
dh
For films obeying Eq(l7) this means that the elasticity must be
some distance to the left of its maximum in the E vs c curve:
dh
de (19)
(20)
On the other hand, for films with <SIT/<Sh> 0, e.g. because of Van
der Waals attraction, the increase in surface area can be more
100
A
max
= A"'n12 = 2n (21)
t 24 no
rupt .. h 3 (oIT/6W- (22)
do
E
dlnA (23)
A final problem can occur after rupture of the film. The hole
102
AP = P
WAh
- P = a (1. - l......)
r (24a)
h
For holes sizes 2r h < h the Laplace pressure is negative,
promoting closure of the hole, while for 2r > h i t changes sign
and promotes growth. The model is a gross oversimplification of
reality in assuming the cross section of the film edge to be
semi-circular and in neglecting the effects of disjoining
pressure on AP, but in a more refined model the two principal
radii of curvature will still be of opposite sign, and this must
lead to a critical hole size at which AP changes sign. The
analogous situation for a film on a solid surface in Fig.9b is
described by:
AP =a ~ 1 - cos a _ 1_ )
h rh (24b)
Critical hole size for these films depends on the contact angle:
h
rcr 1 - cos 6 (25)
confirming once again that holes cannot be formed in wetting
films i f 6=0
a. ). 2fh
.( jh
AIR
b.
\ ~ ]h
.. 2fh
..
SOLID
Figure 9. Simple model for holes in free films (a) and films on
solid support (b).
------ film before rupture.
T = (26)
CONCLUDING REMARKS
This review has been incomplete and may seem to have made light
of several important aspects, such as contact angle hysteresis,
the effects of electrical charge and potential [11,98] and those
of particle shape [52]. These aspects were felt to have been more
than adequately covered in existing literature. Most of the
attention in this review has been focussed on the effect of
surface active materials on interfacial tensions, contact angles
and film thinning. Contact angles can be interpreted and
105
LIST OF SYMBOLS
SUBSCRIPTS
A air
cr critical value
e effective
eq equilibrium
L organic liquid
max maximum growth
rupt rupture of film
S solid
W water or aqueous solution
106
SUPERSCRIPT
REFERENCES
P.L. de Bruyn
(100)
x x x
(110)
A;
x x x
~.
----
-1 ~ r'
'..J
----
-,
r'
',,:
----
.'~-', "-~-,
\. I
~
•
--- (111 )
Figure 1
A + :B = A:B (1-1)
M
s
+ :OH (aq) (M:OH-)
s
(1-2)
:0 + + (aq)
H (O:H+) (1-3)
s s
with M an acid surface site (lattice metallic cation) and :0 a
base s8rface site (lattice oxide ion). s
B A A B
II
Figure 2
III
Fig. 2
also proceed by reaction with a Lewis base surface site when the
water molecule acts as a Bronsted acid by donating a proton
(Lewis acid). The proton will then share the electron pair
donated by the base surface site
H+ + OH aq = H 0 (1-6)
s 2
which also suggesEs that a negative surface charge is obtained by
adsorption of OH ions from solution. If the protoI!. is attracted
more strongly to the lattice anion B than the OH ion is attra-
cted to the cation A ,the solid wills react as a base and become
positively charged s
DISLOCATION
DIFFERENT
SURFACE CRYSTAL
PLANE
FOREIGN
Figure 3
w ydA (2-1)
rev
where y is the reversible work to form a unit amount of new
surface under clearly specified conditions. We note that the
surface area of a solid may also be increased by deformation of
the solid. In contrast to the observations made in fluid/fluid
systems, the two types of mechanical work (surface formation and
surface deformation) are not identical. By increasing the surface
area through a deformation process such as "stretching", the
density of the surface atoms will be changed whereas it remains
constant in a cleavage operation. It is therefore unfortunate
that the intensive property y is commonly referred to as the
surface or interfacial tension. Although this connotation is
quite satisfactory when applied to fluid interfaces, it is
misleading when considering solid interfaces. Only for liquids
123
will y as defined by equation (2-1) be numerically equal to a
surface density of tensile stress.
W yf:,.A (2-2)
rev
It must, however, be clearly understood that in the case of
solids this integrated expression for surface work applies only
if the crystallographic orientation of the surface and the state
of strain of the solid adjoining the surface are not altered in
the process. The former condition can always be realized and the
latter condition will require only a second order correction
especially when the solid is at all times subjected to a uniform
hydrostatic pressure.
r
U TS - pV + I~ini + yA (2-6)
1
r
A _ U - IS + pV I~in. (2-7a)
3 1
125
r
A G - LJ.l.n. (2-7b)
31.1.
(2-7c)
This function has also been used by Overbeek [5]. With the aid of
equation (2-5) the following expression for the complete
differential of A is readily obtained.
r
dA - SdT + Vdp - LnidJ.l. + J.lldnl + J.l2dn2 + ydA (2-8)
3 1.
(2-9)
_(6A)
y -(6A) nl,n2,T,p,J.l k *I,2 (2-10)
r
B =U - TS + pV - tPini - yA = 0 (2-11 )
r
Ady + tnidP i + SdT - Vdp = 0 (2-12)
(2-13a)
r e
tcidP i + sedT - dp 0 (2-13b)
ne
where c~ = -i-
V
is the concentration of component i in the
r
Ady + L[n i _(c~a+ cfv~)]dlli + [S-(s<lv a+ sl\r~]dT
(2-14)
s
nl Ar 1 nl - (c<tv a+ cfv~) (2-15a)
s
n2 Ar2 n2 - c~v~ (2-15b)
s
ni Ar i n. - cfv a(i:l:l) (2-15c)
1
(2-1Ba)
(2-19a)
(2-20a)
(1,2)
c5n
(2)
- 6A Dl,n2jint. (2-18b)
s(1,2)
s
(2-19b)
(1,2) _ c5V
T
= (c5A) nl,n2;int. (2-20b)
g
sO,2) =
r
dy =- ss(1,2) dT + T(1,2) dp - Lri(1,2)d~. (2-23)
3 l.
n c ll - n c ll
1 2 2 1
Ady [s - ( - - - - - - ) sa
a
clC2
a
\I vo ll - n c ll n
1 2 2 1 2
+ [V - II ] dp
c2
1r
-[L(n i c II)] d
i ~i
3
(2-24)
nz
r. O ,2) = 1.. (n - (2-25)
1. A i c~
Z
ss(I,2) = ! [5 (2-26)
n c~ - n c~ n
T(1,2) = ! [V -
1 2 2 1
- -]
2
c~ (2-27)
The adsorption equation (2-23) has the same form as the more
familiar Gibbs adsorption equation
dy (2-29)
where (1)
on
ri (-2.)
oA n 1> V , T , \l k f:l
r
X == U-TS-En. \I.
21.1.
f\l 3 r (1,2) d
(T,p constant) (2-30)
o 3 \13
\I
3
r3(l,2)
r max c3 (2-31)
= c* + C3
132
where r is the adsorption density when all the available sites
per unftlxsurface are occupied, the constant c* represents the
concentration in solution at which one-half of the sites are
occupied. The smaller the magnitude of c* the stron~r2)the
adsorption energy. On substituting this expression for r3 ' in
equation (2-30) and letting a3 ~ c3' the integral may be
evaluated with the result.
y - y
o = = RTrmax 1n(1+ c3)
c*
(2-32)
ADSORPTION OF ELECTROLYTES
o (3-1)
(3-3)
(3-6)
(3-7)
r Ag N0 3
- r NaNO
3 (3-8)
+ r NaNO
3
(3-9)
(3-10)
CJ
CJ 0 CJ+
dy =-- dll 3 - - dll 3 (3-11)
F AgNO F NaNO
If NaN03 is present in a much higher concentration than AgN03 it
will determine almost entirely the magnitude of the ionic
strength of the solution.
Equation (3-11) may be rewritten to yield
(3-12)
00 CJo
(3-13)
dy = -"FdllAg+ = 2.3 RT"FdPAg
s(1,2)
g
(3-14)
a+ (3-16)
~ 3 d(a IF) - - d~ 3
AgNO 0 F NaNO
where s(1,2) a+
g -- ~
(3-17)
F AgN03
As dy, dg s (1,2) and dE; are all exact differentials we find from
equations (3-12), (3-15) and (3-16) by cross-differentiation
oa
~ 0
o~aNO
3 ~AgNO
3
(3-18)
136
-6~ j.LC.cm- 2
0'0
-5 .
I
-4
-3
-2
pAg
9 10 11 12
Figure 4
10-1
10-2
11)-3
}~
11
-1
Figure 5
Ionic components of charge in the electrical double layer on
silver iodide at 25 0 C. Supporting electrolyte KN03
0+ = Frr a -FrNO -
Taken from [11] 3
137
( (
(3-19)
(3-20)
M °
x xz/2
(s) + ~xz)
2
H2 0(l) = xM(OH)
z
(s)
(A)
(xz-y)+
where M (OIl) may be mono- and polynuclear positive or
negativeXhydlo-complexes. Under equilibrium conditions it follows
that regardless of the solid phase
-4 -
-6
z -8 -
o
I-
~-IO
I-
z
W
~ -12-
o
u
l!) -14
o
..J
16
o 2 4 6 B 10 12 14
pH
Figure 6
B Fe 3+ +
D Fe (OH)2 F Fe (OH) 3
Taken from [1 7]
139
2 3 4 5 6 7 8 9 10 11 12 13
pH
Figure 7
Variation of so lubi l i ty of a.-AI (OH) 3' gibbsite with pH
3+ -
1,0 Al 1,4 Al (OHJ
4+
1,1 Al (OH) 2+ 2,2 AI 2 (OH)2
+ 5+
1,2 Al (OH)2 3,4 AI 3 (OH)4
0 7+
1,3 Al (OH) 3 13,32 Al 13 (OH)32
Taken from Baes, C.F. and Mesmer, R.E.: The Hydrolysis of Cations,
John Wiley & Sons, New York, 1976
Figure 8
The equilibrium solubility diagram of ZnO.
Taken from dissertation of L. Blok, University of utrecht, The
Netherlands, 1968
140
(3-22a)
(3-22b)
(3-24)
RTa
o
dy 2.3 -F- dpH
a
o dlJ _
F OH (3-25)
141
Jl
5.
-
,
••
~
-6
'0 60 70
Figure 9
Adsorption isotherm ([r H+ - r OH -] vs pH) on rutile in NaCl04
solutions of varying ionic strength at 25 0 C. The results of the
pH drift technique for establishing the pzc are plotted in top
half of diagram. Supporting electrolyte, 0.01 M NaCl0 4 •
Taken from [14]
<70
-9 I'C/cm2 IN
lO-I N
-6
1O- 2 N
-3 1O- 3N
pH
0
11
+3
+6
+9
+12
+ 15
+18
Figure 10
Figure 11 2 3 .5 pH 6 7 8 9
0'0
CHARGE SOLUTION
t DISTANCE
POTENTIAL
o t
Pigure 12
t
CHARGE
SOLID SOLUTION
POTENTIAL-
I SOLUTION
Fig. 12
b) Charge density vs distance and potential vs distance in a double
diffuse double layer with surface charge.
c) Charge density and potential vs distance at the pzc. The space
charge inside the solid is exactly balanced by the surface charge
density.
145
(4-1)
llJ. = ll.
J
+ z .F~
J
(4-2)
a s
].lj (4-4)
ea
~
z.F (4-4)
J
The Galvani potential difference is lrus determined by the
difference in chemical potential ~].lea =].l - ].la, of the lattice
j j
ions which can pass freely through the interface. Such species
are called potential getermining ions(p.d.i). The Galvani
potential difference ~cp a cannot be measured because it is the
electrical potential difference between two phases of dissimilar
composition. For the same reason the chemical potential
difference is not measurable. Changes in the Galvani potential
difference are accessible to experimentation
~(~cpae) = ~cpae _ ~cpae
o
(~].lea _ ~].lea )/z F
j j(o) j (4-6)
(4-7)
E - EO = RT In
z ,F aj
J
and is therefore referred to as the Nernst equation for a
completely reversible solid/liquid interface. The change in the
Galvani potential difference is seen to be completely determined
by the change in the concentration (actively) ~f_the p.d. ion in
the solution phase. For a simple ion~c soli,5! A B the equilibrium
concentrations of the p.d. species A and B in the solution are
coupled by the solubility product thus
a a
aB-(o)
Acpaa _ Acp:a = !T In a~+ = !T In
a
aA+(o)
-
00 = F(z+f x
= -RT 6
d1/lo
zl dIn a
j (4-12)
and therefore
S
!JAg (4-13)
!Jin(Ag)
+ loX
pzc pzc (4-14)
<1 S
Where the potential differences • - . lies completely in the
solid phase and may in principle be evaluated. In any case the
right hand side of equation (4-7) remains unaltered when applying
the equilibrium condition (4-13).
(4-14a)
(4-15b)
-s s se
= d~j = d~j + ZjF dlo' (4-15c)
are often smaller than 10- 21 cm 2s- 1• As the diffusion length will
be proportional to 12D;t, with the diffusion time t, the depth of
penetration of these !"bns into the solid in one day will be of
the order of 0.1 nm or less, dis tances much smaller than the
thickness of the space charge region. Equilibrium of the solid
particles suspended in the solution during adsorption
measurements (changing concentration of p. d. electrolyte) will
therefore involve at most the outer surface layer of the crystal.
and the more mobile Ag+ ion in silver iodide will diffuse farther
in the crystal in this time period. When small AgI particles are
allowed to equilibrate with the solution phase, thermodynamic
equilibrium will therefore be established within a couple of
minutes not only between the interface and the solution but also
between the solution and the solid interior. The Nernst relation,
equation (4-7) should therfore be obeyed as is demonstrated by
the existence of reversible silver halide electrodes. For the
silver iodide/soplution system at room temperature we may then
write
0.059(pI-pI ) volts
pzc
dy
S
sQ d\1 j RT Q
dl14> jJ
= zjF + ~F
dl n a jJ
j (4-18)
The preferred model for the adsorption of p.d. ions (H+ and OH-)
is a three site model in which the charged sites are created by
dissociation of an amphoteric surface group MOH according to two
connected adsorption steps
..
+
MOH + H+(aq)
K+(K ) H K (K )
1 - 2
MO + H+(aq) (4-19)
The formation of a negative surface site is indicated to occur by
desorption of a proton, it may equally be regarded to form by
adsorption of an hydroxyl ion. Thermodynamic equilibrium between
the surface and the solution requires
154
I = 6n + 6+ + 6
-
(4-22)
or
0'
(l 0_ = 6
= __ - 6 (4-23b)
o 0' +-
max
where 0' = N e is the surface charge when all the available N
sites a~xoccu~ied by positive or negative species. s
N !
s
w = c !c !c ! (4-24)
+ - n
The total number of arrangements for the distribution of c ,c ,c
species on N distinguishable sites per unit area; Thi~
expression may snow be used to evaluate a configurational J30] or
entropic contribution to the potentials Iln , 11+ and 11. The
complete partition function (Q) for the surface layer ~y be
written
155
A kT In Q
and
lli
- = (6A/kT)
kT 6ci
T,clf:i
a+
-kT (Hnw) kTln
6c+ c- ,N s I-a -a
+ -
a
-kT (Hnw) = kTln
6c- c+,N s l-a~ (4-25)
+ -
where we have employed the Stirling approximation Inx! = xlnx-x.
On utilizing the results of (4-25) we write
-0 + kT a
ll+ ll+ In l-a+:e"
+ -
a
ll_ j';~ + kT In I-a :a (4-26)
+ -
-0 .
where the term II 1S the remaining part of the electrochemical
i
potential assumed to be independent of a. On introducing these
expressions for ~ and II and the appropriate expressions for ~+
+
equilibrium (equation (3-20c» we find after rearranging terms
a
+ -0 -0 -0
-In -a- + 2 In ~+ = - (ll_ + 2 llH+ - ll+)/kT
- b.'G0 /KT
In K.r~ (4-27)
156
MOH+ + MO + 2 H+ •
2 +
(4-29)
where
K K = exp(~+ - ~_ - 2~0 )/kT
1 2 H + (4-30)
-2F1j1 /RT
k+K_e 0
pH t(pK + pK )
pzc 1 2 (4-31)
(4-32)
KI 62 0-26 )2
n 0
K 6+6_ 2
2 6 (4-33)
0
therefore
1
6
2+1K IK
I 2 (4-34)
Table 1
(4-35)
a
o
6
o
Deviations from the Nernstian equation at low surface charge are
seen to be most serious when 6 is very small as would happem
when K is small (see(4-34) andtT~le 1). The exact expression for
the function f(K,a ) = (6 16) may be found by solving equations
(4-22),(4-23b) and o (4-33) +
as-was done by Dousma (31)
158
s + A+ + S
.. +
159
+
The adsorption of A will take place on site S and convert it
into S+ site. The charge of the surface will then increase by one
unit Whereas the difference (C+ -C_)F increases by two units.
These considerations show that
a
max
and
or
(9+ - 9_) = (29+ - 1) - a /a
o max = a 0
If we further define a equilibrium constant K3 for the reaction
S + A+ + S K3
- s + +
where [A+] = [A+] exp (-y ) is the concentration of the p.d ion
o
+ s
A next to the surface then the following relations are readily
obtained
-+ .
[B-]
K3 K pzc
[A ] pzc sp
and
9 .. t
0
[A+] = [A+] 9 t
(-±.) exp (e1jl0 /kT)
pzc 9
160
e:e: (5-1)
o
ao =-0-1jIo
00 &&
C o o
-0-
<iTo (5-2)
where
(5-4)
is the (volume) charge density and ni(x) is the concentration of
ions of charge zi e at a point in a plane parallel to the solid
surface at a perpendicular distance x from the surface. To
evaluate 0d we make use of the Poisson equation in the form
~2~= _ p(x)
e:e:
dx o (5-5)
°o - ££
o (5-7)
~2~
(5-8)
dx
Isn
kT
(d1l1) = _ _0 _ sinh (zeW 12kT)
dx ££ 0
(5-9)
o
x=o
with y = zW IkT
o 0
o KW0
00 = ££ (5-11)
162
t
where K
(5-12)
2", 2
e "zino(i)
K2 =--7'=~~
EE kT
o
For large double layer potentials when zeW /2kT > 5 or W > 250/z
mV (T = 250C), sinh(y /2) ~ texp(y /2) 0 0
o 0
thus
- 0d = ILEE n kT exp(y /2) (5-13)
o 0 0
(5-14)
2zen o
111 + CD =
o IC (5-16)
da
o
d1llo
to yield
a
d
=- 11.74/c
o
sinh 19.46z1ll
0
(8££ kTn
o 0
)t sinh(zeljld/ 2kT) (5-19)
(5-20)
and
(5-21)
or
166
0'0
'+'0 o~p
I
I
I DIFFUSE
LAYER
--'l--DISTANCE
'Tl..
t ~--=~--i\.o
Figure 13
eYO Oft
I
I I
I CYd
':HP:
I
<PO
IO:HP
I I
r
I J
I I
I I
'Pfl I
I
I
<Pd
.. DISTANCE ~
~
I
I
I
I
Figure 14
(5-22)
(5-23)
As the inner region of the double layer does not contain any free
charges, the potential will vary linearly with distance and we
may write (see equation (5-7)
(5-24)
a
o
(5-25)
ao
o=-+
~
C ~d (5-26)
(5-27)
An order of magnitude for C may be calculated.For water as sol-
vent we let E. ~ 10,a valuestlose to that for dielectric saturat-
ion,and choos~ d ~ 0.3nm to find C ~30~F/cm2.As C increases ra-
pidly with increasing surface char~~(equation[5-221)tthe capacity
of the double layer at moderately large values of a will be det-
ermined mainly by C .A plot of C versus a will ~ow the char-
acteristic minimum ~~lue of capacity at theO pzc(equation [5-18])
for low electrolyte concentration and rise to a plateau value
about 30~F/cm2 on both sides of the pzc. The assumption is made
here that C is a constant.Although qualitative agreement bet-
ween theory stand experiment(C vs a ) is obtained,it was assumed
that the lack of quantitive agreemen~
169
As pointed out by Mackor [38] one may also elect to retain the
concept of a constant Stern capacity C* and account for the
st
experimental facts by the dependence of the A potential
difference on the surface charge. Certainly the ori~tation and
polarization of the polar solvent molecules must be affected by
changing field strength. Mackor's suggestion is then to write
1 1 + .,!AX + 1
C= ~
st
do
0
Cd
(5-28)
d1/l - dAX
o
Suppose now that the dipolar molecules adsorb by orientating
their positive poles to the surface then 1/1 will change to more
negative values and therefore also 1/Id proviSed that 11/10 1 was not
already large. If this adsorption took place in a system
initially at the pzc this implies then that the pzc will be
restored after adsorption of the dipolar species only by raising
the concentration of the p.d. cation in the solution.
where °
may even exceed in magnitude 0. Strong specific
adsorptiSn implies that at the pzc 0
Of:! = - °d (5-30)
(5-31)
(5-32)
e:oe: i (5-33)
Ki "'--d-
then
CI '" _a_ and C = (d-aL
Kid 2 Kid
whereas at iep
1/1o -- 0
o/C I
For the charge density in the diffuse layer we may still write
for a symmetrical electrolyte
2e:e: KkT
0d '" - 0 sinh ze1/l/2kT
ze (5-34)
(5-35)
o(a) 9
~i = Pi + kTln - -1-9
-- (5-36)
where the second term on the right hand side represents again an
entropic contribution to Pi and 9 is the fraction of the
available ~ites in the IHP occupied by the ion on the basis of
one ion per site. On applying the condition for equilibrium we
deduce
o(a) o(L)
_9_ - C [exp-(p
1-9 - -p )/kT]
i i i (5-37)
o
Ci exp (-AG-ads/kT)
o
where 6G d is a standard electrochemical free energy of
(specifier sadsorption, C is the equilibrium concentration
(neglecting activity coefdcients) in the bulk solution. Solving
for 9 we get
ri C
9
ri(max) = Ks+ Ci
(5-38)
0
where K exp (AG d /kT).
s a s
(5-39)
173
= eiB.exp(-z.e~~/kT)
~ ~
(5-40)
where Bi is an equilibrium constant, i.e. the number of ions unit
area for unity concentration of ions of type i and vanishing
potential difference. The exponential term in equation (5-40)
accounts for the difference between the adsorption of an
electrical neutral and of a charged species. Even at low surface
coverage the adsorption density of ion i need not be directly
proportional to its concentration in the solution phase.
Suppose that only univalent ions are present of which only the
cation i is specifically adsorbed. If we con~ider now the
adsorption of species i at the pzc then d~ = d~ and according
to equations (5-7) and (5-9) 0
8e kT t
_ (___0___) sinh(e~~/2kT) (5.41)
££
o
(5-42)
where
-1
y 2 sinh OX} (5-43)
and
174
x = r i t (5-44)
i(PXC)~2££ C kT)
o 0
If X«1. we have
(5-45)
that is. the amount of ions of type i chemisorbed per uni t area
at the pzc is proportional to their concentration in the co-
existing solution and the presence of the electrical double layer
yields only a correction of minor Wportance. This implies that
the p. d. across the double layer ill/I = ill/I is less than 25 mV at
room temperature. 0
r i(pzc)
whence
r i(pzc)-- c il/3 c 0l/3 (2Bi ££ 0 kT/e 2)1/3
(5-46)
One may now combine the t~eatment _of the three site or amphoteric
model for adsorption of Hand OH ions on oxides and the double
layer theory to calculate charge-pH and potential -pH curves. The
calculations make use of three equations [31]
exp(zel/io/kT)f(K,~o)
(K 1K2 )' (4-37)
,',
"'0
= "'d
'"
+ 0 / C
0 st
(5-26)
1.0...-------------------------r
"
.....
......
a ......
----...... .......
...... .......
8.0 10.0
pH
Figure 15
f 2.0 ,,
g 0 ,,
h -5.6 ,,
177
d c b a
¢d (mV)
== (pH.
p. z. c.
_pH)
Figure 16
1.0~------.,----------------....,
a:Cstern = 5 F/m 2
b:C =00
stern
p. z. c.
Figure 17
(pH -pH) from the pzc when pK is negative (K small) that is when
theOfraction of charged sites at the pzc (a ) approaches a value
of t (see Table 1). All the curves are sj>mmetrical around the
pzc. The continuation of the curves beyond pH = 9.4 is therefore
not shown in Fig.lS. A change in the pzc at c8nstant pK (a ) will
give curves displaced parallel to those shown for pH = 9~4. The
calculated dependence of land Wd on pH are ilfustrated in
Fig.l6. It is interesting toO note the deviation of the calculated
curve (W vs pH) from the Nernst equation (dashed curve) near the
pzc at Righ pK values (low a ). Except at high ~pH (pH -pH)
values when charge saturatio~ (a ) is reached the PN~rnst
equation is seen to be obeyed ratherma~ll for low pK's. A similar
behaviour is also noted at lower and perhaps more realistic
values of C (e.g.O.S F/m 2 ). It would appear therefore that only
for 0 ao st 0.08 noticeable deviations from the Nernst equation
are to be expected for the chosen set of parameters (K 1 ,K2 ,
etc.) •
The results obtained with the two-site model of Stol [33] are
included (stippled curves) in Figs. 16 and 17. We note that the
two-site model yields curves nearly identical with those derived
from the amphoteric model for e = 0.5. The two-site model
proposed by Stol might !1-e prefe.!ab~y applied to the description
of the adsorption of Ag and r on silver oxide. However, this
model also gives adsorption i.sotherms which are sYDDDetric around
the pzc, whereas asymmetric experimental curves are found for
silver iodide (see Fig.4). A possible model which could account
for this aSYDDDetry would be one which features four distinct
sites. Such a model was suggested by Healy and White [27]
although not in this context. This model when applied to Agr can
be described by the surface reactions [31].
(aq) t S
K
sp
nAg + nS NS/2
+
nr + nS N /2
s
C1 =(n - n_)F
0 +
may be solved to obtain theoretical isotherms. The sites S+ and
Sr and the sites S_ and SA are not identical as would be the
case for a two-site mOiel.g This distinction implies that, for
example, an adsorbed Ag ion is distinguishable from a surface
lattice ion.
d(z+r x - z r y ) do
o
C • d(pY.pY ) (6-1)
d(pX - pX)
pzc pzc
182
~/crmax
-0.05
8 9 10
= pH
Figure 18
Calculated plots of O%max vs pH in presence of specific adsorption
and varying ionic strength after Dousma [31]
a: 0.001 M b: 0.01 M c: 0.1 M d: 1 M
Arrows indicate position of pzc
The following parameters were used in making the plots:pKl = 5.1,
P K2 = 10.7, this fixes pzc at pH 7.9 in absence of specific
adsorption
Cl = 1.4 F/m2, C2 = 0.2 F/m2 2
0max = 1.2 C/m2 in agreement with 8 sites/nm
pK3 = 10.5, pK4 = 9.0. This choice allows for strong specific adsorp-
tion of anions. A decrease in pK3 below chosen value results in in-
creased adsorption of cations; a decrease in pK4 results in a de-
creased adsorption of anions.
183
80
IjJd
0.001 M
pH __~~---------
Figure 19
C
(6-2)
The most reliable pzc data are obtained by two experimental met-
hods.(a)In the absence of specific adsorption the a vs pX curves
at different ionic strengths will have a commono intersection
point. If specific adsorption does occur at high ionic strength
the pzc will shift and will be determined as the intersection
point of the adsorption curve with the zero charge axis deter-
mined at low ionic strength or in the absence of the chemisorbing
ion at a fixed ionic strength. (b) Berube and De Bruyn [14] proposed
an alternative method based on the consideration that the pX of a
solution containing an indifferent electrolyte will change upon
the addition of the uncharged solid except at the pzc(see Fig.9).
I t is essential that the dry solid, for example, an oxide, does
not contain free acid or base before being added to the solution.
settled
calomel electrode A Isuspension I supernatantlcalomel
of solid liquid electrode B
An extensive review of pzc and iep values for simple and complex
oxides have been made by Parks [46,47]. This author did not
always distinguish between pzc and iep measurements. Honig and
Hengst [45] have tabulated iep values for a large number of
slightly soluble inorganic salts measured by the suspension
185
Attempts .have also been made to correlate the pzc of oxides with
their bulk properties. One method of predicting pzc' s of simple
oxides and hydroxides [50] is based on locating the pH of the
minimum solubility of the solid in solubility diagrams (Fig.6). A
second method due to Parks [46.47] is largely based on an
approach similar to that used to estimate the acid strength of a
186
Adsorption isotherms
Figure 20
Some experimental ao vs ~pH curves for 0.1 M 1:1 electrolyte.
For comparison the adsorption zurve for AgI is included, the ~pAg
scale is the same as ~pH.
- - - - - - - - TiO iNaNO
2 3
. . . . . . . . aFe 20 3i Kcl
_ _ _ _ y-A1 2o/NaCl
_______________ Ti0 2KN0 3
_ • _ • _ . _ a-FeOOH/KCl
Taken from [12]
188
The solid state model which has also been applied to the silver
iodide system, emphasizes the solid state properties of Ag1 by
expecting the defect structure to play an important role in the
formation of the double layer. For the interface ionic
crystal/electrolyte solution this leads to a double diffuse
double layer, modified with in addition a fixed surface charge.
This surface charge is due to a difference in free energy
formation of intersitials and vacancies in the bulk of the
crystals compared to their formation at the surface. Honig [61)
was able to obtain a good fit with the experimental adsroption
curves by adjusting the values of two imporant parameters of his
model; the fraction if the number of lattice defects in AgI of
0.17% and the potential difference between the solid surface and
the solid interior of -53mV both at 20DC.
REFERENCES
G.J.Jameson
INTRODUCTION
The cine film of Spedden and Hannen showed that when larger
particles struck the bubble, it was possible for the bubble's
surface to deform elastically. The particle was seen to bounce
off without making contact, even if it was hydrophobic, an
observation which has been confirmed many times since. This
observation led a number of authors, notably Sutherland [7]
Philippoff, [8] Evans [9] and Eigeles, [10] to postulate that
there was an "induction time" necessary, to allow the thin liquid
layer between bubble and particles to drain away and permit
coalescence to occur. If the "induction time" were less than the
"contact time", i.e. the time available while the particle
approached the front of the bubble, then moved sideways and
travelled around the nose, coalescence could be assumed to occur.
CaimllK,I and
straiQ~n9
HCtIon
Injection line
LoacIInQ
ella
WorklnQ MCtIon
Drain
Air
bleed
line
Line to initially
fill caIurM
Ca)
e---e-
4
o 3 4
Ce)
K = p d 2 U/9~ db (1)
P P
which are obtained in flotation (K « I).
E (2)
c
where db is the radius of the bubble, and d is the radius of the
"tube" ahead of the bubble in the flow field, within which any
particle which is to collide and coalesce with the bubble must
initially have found itself. Any particle distant further than
(d/2) from the axis of the system will then escape collection.
E
c
= G/(l + G) (3)
2
where G = (p
p
-p) d g/18~U,
f p
and also with an expression of Fonda and Herne. [13] However, the
simple result of Sutherland: [11]
(4)
t. =n (d 3 P 112Y)! (5)
~ p p
due to Philippoff [8] and Evans [9] was found to give induction
times about one-half of those observed.
g.--- Microscope
Sample
.--:-:-~:qC
Vacuum '"
"'"
1rCollection
Three"'.. way
,,
ta,!s . J section
Constant
,
head water ~=.:;-,
.(I)
,::":',
Suspension
container
-- ---
Rotating tap for
bubble production
Gas waste
Figure 3. Apparatus of Anfruns and Kitchener [14] for
determination of rate of capture of particules by
single bubbles. A, bubble generator; B, inlet for
suspension; C, outlet for suspension; D, optical cell
for observing particles attached to bubbbles; E,
preparation vessel.
If the drainage time of the thin water film was the cuase of the
low collision efficiencies of the spheres, then Anfruns and
Kitchener argued that one ought to be able to reduce the drainage
time by removing one of the factors tending to keep the surface
of the bubble and the spherte apart, namely, the electrical
double layer at each interface. Accordingly, they added 1 M KC1
200
(0)
••
0·02
0
c: 004
0
u (b)
~
0
<...> 003
002 . ••
• •
0,01 •• • ·t
00
.• 00 0
",
0
,
0
00
•
,0
0 ,0
05 06 0 08 09 70
Bubble diameter, mm
- - - - Stirrer
Foam '\
suction
plate
Baffle
~~~~~m~?--
"
Porous
glass
frit
Nitrogen
Figure 5. The flotation cell of Reay and Ratcliff. [17]
(6)
2 3
k a: (d/d b ), (7)
Fine particles
The reasons for the low recoveries at the low and high diameter
ends of the spectrum are quite different. With small particles,
we have already seen that there is a strong dependence of the
flotation rate constant on the particle size. Equation (7),
derived for collection by bubbles rising in a stationary fluid,
predicts that the rate constant should vary as d 2 • while the
experimental data for such systems (Reay and ~cliff; [17]
Collins and Jameson)[18] suggest that the exponent should be 1.5
approximately. Traher [21] quotes results from Gaudin et al [22]
and Morris [23] which indicate that in flotation cells with
conventional impellers. the rate constant varies linearly with
d •
p
203
90
Z 80
o
;::
{) 70
~
U.
W 60
N
iii
::; 50
oa:
u.
>-
a:
w
~ 30
{)
..
W
a: 20
'0
0~'--~--~~'~0~2~0---5~0~'~00~2~00~-5~00~·100·(
AVERAGE PARTICLE SIZE (MICROMETRES)
For fine particles then, it seems that a plausible reason for the
low recovery is related to the low rate of flotation. If the
flotation time is increased, the recovery of the fine particles
increases also, but in a practical case, the quantity of gangue
entrained and removed in the froth would increase as well, giving
rise to a reduction in the grade, i.e. the proportion of valuable
material in the conce~trate.
The work of Reay and Ratcliff, and Collins and Jameson, suggest
that a way to improve the rate of flotation of fine particles,
would be to use smaller bubbles. The bubbles in conventional
flotation machines are typically 0.5 to 2mm in diameter, although
the available data are meagre. [2] For bubbles in free rise, at a
constant gas rate the rate of flotation should vary inversely as
d~, so there would be real advantages in using bubbles in the
range 50-100~m in diameter. Such bubbles are produced in
dissol:ved air flotation, such as in the nozzle developed by the
Water Research Centre, Medmenham. Rees et ale [24] show that
their nozzle gives bubbles with a mean diameter of 80~m
approximately, with air at a saturation pressure of 485 kPa.
Large Particles
Cp - \0 , 6 ... riable
E - ~9 -10 4 ",,2 -S-, t-----T---+----I
gF- 2,5g·",,-3
I
10~--+-+~-+--t-
I
~ u v, - 2Scm·s~ I
&. 0 v, - 37cm-s·f
-~
II
I
I
I
I
I
10 12 14
pH ... Iue
The charge on the bubbles was measured in the same type of cell,
208
One of the concerns one must have here, is whether or not the
bubbles which are generated by a pulse of current, are in
equilibrium with the liquid, especially regarding the surface
concentration of adsorbed surfactant. Elsewhere in this volume,
experimental evidence is given which shows that the rise velocity
of bubbles created in almost pure water decreases gradually with
time as the surface of the bubble becomes contaminated with trace
quantities of dissolved materials. In the experiments of Collins
et al., however, the concentrations of surfactant were far from
209
FROTH STUDIES
The phenomena which take place in the froth probably have little
effect on the yield of values, because there is little evidence
to suggest that there is a substantial return of values from the
froth to the pul.p by rupture and disengagement from the bubbles
in the froth. However, the froth effects have a very large effect
on the grade, i.e. on the mass fraction of values in the
concentrate. This is because the practical measures which can be
taken to inc.rease the mass of values recovered from a cell, such
as increasing the residence time of the pulp, lead inevitably to
an increase in the quantity of pulp entrained into the froth and
recovered with the concentrate. Since the values normally
represent only a small mass fraction of the gangue present in the
feed, a disproportionate quantity of gangue ends up in the
concentrate as flotation time increases. This effect is shown
clearly in the graph from Hemmings, [35] Figure 11.
211
30
25
20
-.:.
CO') 15
0
~
III 10
"...
III
C)
5
100
Recovery W0 3 0/.
SlOE ElEVATIOtI
FROTH
INTERFACE SLIDE
(IN OPEN l'OSITiON)
PULP
IMPELLER ~ STATOII
VARlMLE
SPEED
MOTOR
-CENERA1OR
E
u
,.: 15
:r
!2
'"
:r
:r
b
...a: 10
O~____~____~~~~~~------
o 50
CONCENTRAnON.9 r '
strong effect of sample height above the level of the pulp in the
cell. Near the base of the froth, the mass ratio of values to
gangues was approximately 2.5, whereas at the top of the froth,
it was 4.3. In the feed, the ratio was 0.11. The water content,
measured as g water per unit volume of froth in the horizontal
slice, decreased by a factor of ten, for a total froth height of
20cm. Increasing the air flowrate increased the wetness of the
froth, and there were also small changes in the grade of the
hematite concentrate in each slice. At the base of the forth, the
grade was lowered by the increased air rate, whereas at the top
of the froth column (20cm height), the grade was actually higher.
The overall recovery was slightly higher at the increased air
rate and the overall average grade was slightly improved.
SAMPLE VACUUM
COLLECTORS SUPPLY
VARIABLE
SPEED
MOTOA
FLO-S TAT
AlA
SUPPLY
'0
";;;
X
ESTIMATED FROTH MOBILITY STRUCTURE X
5
...
It
20
..
..,
oJ
"
U
'";i
g
.,
co:
>
0
+----TAILINGS OVERFLOW
SLURRY PHASE ---f-:"''' WEIR
SANDS GATE
AIR
Figure 16.The deep flotation cell of Moys,(42) for both batch and
continuous tes ts. Dis tance between sample points is
5cm.
---.
~-I+-~-:::::::""--i'1
~~m+iH-~-
avila....
DUWmotar
.......
When the contact angle was less than 90 0 , the two circular lines
of contact formed by the section of the upper and lower
interfaces,did not actualLy meet on the surface of the sphere,
lllumllllltion
° °
in the liquid. It was observed that when the contact angle was
be.tween 82 and 98 roughly, such particles did not rupture the
film, but for all other contact angles, the ability to rupture
films was identical to that of spheres.
219
Time, m.
Time, m.
40
81
13,5
68
- - 82
70 14,7
274
24,5
423
116
~---"""::::::::J 554
-;-~-O9-_-
A
8
---------r--~---------
w
Time,
ms
80
12,0
97
14,9
_101
----- 97
16,3
-103
- --- 97
17,7
19,1
19,8
is fed. The froth rises to meet the deflector and slides smoothly
forward on the thin liquid film on the underside of the porous
plate. Some liquid is also directed to run down the vertical
walls of the cell, so that froth does not adhere here, either.
Another Leeds design has been described by Dell and Hall, [54]
which has a bottom-entry impeller, thus leaving the top of the
cell open and unimpeded. The layout is shown in Figure 23. The
authors suggest that fro.th can be scraped off at a single rapid
stroke, and that with this arrangement, there is no need for the
sweaty porous plate in their previous model. The design would be
particularly valuable for work on the entrainment and drainage
u-tube
m",nometer
Makt:-up
water Inltt-
Horizontal
ter
Linkage
control
corner
piec(ls
000 0
Bas.
drive unit
Tochometer Drive
pick-oft bpi!
Figure 23. the leeds open-top cell (Dell and Hall. [54]
Locating hooks
Scraper
Deflector
block
Clamping
screws
Cell
Impeller
NOTATION
REFERENCES
32. Sato, Y. ,Murakami, Y., Hirose, T., Yamamoto, H., and Uryu,
Y., Removal of emulsified oil particles by dissolved air
flotation, J.Chem.Eng.,Japan, ~ 454-459, 1979.
H.L.Shergold
Department of Mineral Resources Engineering
Imperial College, London,S.W.7.,England.
INTRODUCTION
aperture size
about I Scm
maximum paJ1.ide
lize.boutS~m
aperture sin
about Ian
r~uent1yless
thanl~..
dilpolal of dispoOll of
.w.bIo pn>d.ds ...... pn>ducts
Y - Y
Cos S = sv sl
Ylv (1)
The work required to separate liquid water from the solid surface
and replace it by an adsorbed water layer in equilibrium with
saturated water vapour (Wsl ) is given by the Dupre relationship.
(2)
or WS~ < Wco where Wco is the work of cohesion of the liquid (149
mJ m- for water). Thus a the·rmodynamic condition for flotation
is that the work of adhesion of the water to the solid must be
less than the work of cohesion of water.
Solid
MINERAL/WATER INTERFACE
MOH sur f + MO + H+
+ surf aq
(4)
+
MOH sur f t MOH2surf
_(5)
where M denotes a surface metal site and H+ and OH ions are
potential determining. Parks and de Bruyn [1] have postulated a
different mechanism for the charging of oxide surfaces which
involves partial dissolution of the oxide and the formation of
hydroxylated metal species in solution, followed by adsorption of
these complexes. For example, for the metal oxide ~03:-
Z35
M(OH)3-m + M(OH)3-m
+
m(aq) m(surf) (8)
12
10
8
IC'I
~ 6
0
E
~
4
"'0
~
2
....
-.g
c ~
11\
0
2
I
:::c
0
~
4
0
+
:::c 6
8
10
12
3 4 5 6 7 8 9 10 12
pH
Figure 3. Abstraction of H+ or OH ions by Swedish hematite in
KCl solutions [2 ]
Oxide pzc(pH)
quartz, Si0 2 1-2
cassiterite Sn02 4.5
zirconia Zr0 2 4
rutile Ti02 5.8
hematite(natural) Fe 20 3 4.8-6.7
hematite(synthetic) 8.6
corundum Al203 9.1
magnesia MgO 12
6- Pyrosilicates
1 ~ (Si20?)
Metasilicate
2 ~ ~(Si03)2- chains
~ pyroxene
¢*
(Si03)~n- Metasilicate
rings
Metasilicate
2~ (S;40,,1 6- chains
(amphibole)
marked effect and the i.e.p. of Al203 was shifted from 9.6 to 8.8
after storage at pH 10.0 for 16 hours in glass vessels.
I I
-Si-O- + H+
-Si-OH +
+
Isurf Isurf (9)
I + -H+ I I
-M-OH + -M-OH -M-O
12+ Isurf Isurf (10)
surf
Breakage of an orthosilicate is more likely to give rise to a
metal cation site than breakage of more complex silicates, which
should lead to higher p.z.c. values for orthosilicates than those
obtained for other silicates. The p.z.c. values shown in Table 2
suggest~ that, in general, this is the case. The p.z.c. values of
the pyrosilicates, pyroxenes and amphiboles would be expected to
be near that of quartz, because of the predominance of silanol
240
sites over those of the metal hydroxide.
b) Salt-type minerals
(11)
+ COZ aq
COZ(g) K =3.38 x 10- 2 (14)
+
10-10~_~_~_--=-_---=_-:::-----:~--=---:;!.
5 6 7 8 9 10 11 12 13
pH
Figure S. Solubility of calcite as a function of pH in a closed
container
c) Sulphide minerals
underlying sulphides.
Eh
-0·5 Pb
+
H2S
Pb+ HS-
-1-0
0 pH 7 14
Figure.6. Electrochemical phase diagram for galena (Equilibrium
lines correspond to dissolved species at lO-4M)[35]
Moignard and Healy [9] showed that acid or alkaline i.e.p. values
were obtained depending on whether the sample was washed with
acid or alkali. It was suggested that the ZnS was oxidised to SO
under acid conditions and to Zn(OH)2 under alkaline conditions
and that the i.e.p. values representeo surfaces covered by these
compounds.
d) Molecular crystals
Collector Structure
Non-sulphide flotation
0
II
Carboxylate R - C
\
0
+
Na
0
II
Sulphate R - 0 - S - 0 Na+
II
0
0
II
Sulphonate R - S - 0- Na
+
II
0
H
1
Hydroxamate R - C- N
II
0 0
1- Na+
Amine R NH/Cl-
Sulphide flotation
0
II
Xanthate R - 0 - C
\_+
S K
Dithiophosphate R - 0 S
\ II
p
I \
R - 0 S K+
Dithiocarbamate R S
\ II
N- C
I \_+
R S K
247
zero
zeta
potential -40
CHMC
I I -30
-10 I I
10 I I
-20>
I E
I
I -10 c;
cu I :.::c
C
E _11
, 10
I
I
I
0 cu 0-
Co
-
~ I
'Vi I
10 c
c cu
~ 10 N
20
30
40
SO
1013L--~-::--_-l----'-:----':""--L-;------I
10- 5 10- 4 10- 3 10- 2
Equilibrium concentration of sodium dodecyl
sulphonate( mole/litre)
Figure 7. The adsorption density of sodium dodecyl sulphonate and
the zeta potential of alumina as a function of dodecyl
sulphonate concentration at pH 7.2. {after Wakamatsu
and Fuerstenau[14].
RCOOH +
+
pK
a
= 4.7 (21)
then S K { Ka + I} (23)
[H+ ]
a) Chemical:
b) Mixed potential:
ROCS 2- +
+
(ROCS 2 )2 + 2e
(30)
and a cathodic reduction of oxygen
t 02 + 2H+ + 2e +
+
H2O (31)
c) Semiconductor:
In the case of galena it has been shown [34] that around the rest
potential, xanthate is chemisorbed by a reaction of the type
+ (32)
(34)
.. (35)
257
Cationic flotation
Mineral HF treat. Fluoride addn.
pH 3.5 - 10.0
Anionic flotation
Mineral HF treat. Fluoride addn.
pH 3.5 - 10.0
+ (36)
+
\ Al - OH + SiF6 2 - ++
\ AI- -
SiF 6 + OH
/ surf / surf (37)
and that the complex would ion exchange with surface hydroxyl
groups
. + + ++ +
surface latt1ce cations (Na,K and Ca ) for H ions.
Kitchener and Warren [42] considered that the SiF 6 2- ion was not
the activating species, bcause they argued that an increase in
the negative zeta potential of feldspar was obtained at fluoride
conce!!trations too low to form significant concnetration of the
SiFh 2 ion. Indeed, the concentrations used by these authors were
a ractor of ten lower than that considered by Read and Manser
[38] in their calculations of the complexes in solution. It would
therefore appear that although the SiF6 2- ion might be important
at high fluoride concentrations, some interaction between the
fluoride and the feldspar surface must occur at low
concentrations. Kitchener and Warren suggested the adsorption of
F- ions on aluminium sites. Possible reactions might be
'AI - OH + F
\
+ Al - F + OH
+
(40)
'surf 'surf
'Al - F+F +
+
\Al - F2
-
(41)
'surf 'surf
\
Al - OH + F + -AI
, OH
+
'surf \
surf F (43)
-Al
,OH
+ F + -Al
, OH
+
\ \ -
surf F surf F2 (44)
Although a lot of emphasis has been placed on the activation of
feldspar at low pH values, fluoride is also adsorbed at higher pH
260
values to give more negative zeta potentials. The presence of
fluorosilicate under these conditions is unlikely, because the
dissolution of the silicates is low and therefore an alternative
interaction mechanism is required. The most likely is that
suggested previously, where the fluoride ion interacts with
aluminium or other polyvalent metal sites in the silicate
surface. Such a mechanism would explain the increased negative
zeta potentials, and hence increased flotation with amines, and
also the depressing role that fluoride has on the fatty acid
flotation of silicates.
10- 4
A1 3+ AI (OH)3
(5)
--
IQI
~
10-5
~
J!! 10- 6
0
E
c::
10-7
-
0
+=
c
~
c::
QI \
u
c:: 10-8 \
~
0
\AI(OH)i
\
10-9 \
\
\
10-10
0 2 8 10 12 14
Figure 8. Logarithmic concentration diagram for I x 10-~M AlGl 3
pH range
2 - 7
6 - 10.5
3 - 8.5
8 - 12
11
12
261
OH OH •••• O - eu+
\ I \ I I
Si + <ll(OH)+ + Si H
I \ OH I \
OH
surf
\ /H +
Si + <ll(OH)+ + (45)
I \
OH
James and Healy [44] have proposed that the relative hydration
energies of the hydrated cation and the hydroxylated cation may
be used to explain why the hydroxylated metal species is involved
in the adsorption process. For the highly charged parent cation,
the energy involved in removing the hydration sheath, to allow
262
°
where AGadsi is the free energy of adsorption of the i th species
and AGO and AGO h ' are the contributions from coulombic and
chemicffUlnteracti'bn'i;~ James and Healy [44) assumed that AGghemi
would be independent of the cationic species so that adsorption
would not be through the OH group by hydrogen bonding, but
through the metal ion itself. Thus whether or not AGOadsi is
ne~ative, will depend on the relative magnitudes of AG80uli and
AGcouli ' These authors calculated AGOsol v . using a model in which
the aasorbing ions, with its primary h~dration sheath intact,
moves from the solvent up to the IHP, where the permittivity (E i )
is lower, and in the process losses its secondary hydration
sheath. Several approximations had to be made to estimate E., but
l.
a good agreement was obtained between the calculated and measured
metal adsorption densities.
+ OH - 4.27 (48)
+ - 1.17 (49)
+
:c
SHOH) 4 + 20H + Si0 2 (OH)2 + H2O. PS2 - 5.44 (SO)
+
2-
4Si(OH)4 + 20H +
+
Si 4 0 6 (OH)6+ 6H 2O. pS24 = 14.9
(51)
266
It-
4Si(OH)4 + 40H- ...+ Si 40S(OH)4 + 8H2 0. p~44 23.6 (52)
2-
2Si(OH)4 + 20H- ...+ Si 20 3 (OH)4 + 3H 20. p~22 .. -9.9 (53)
1
10
'I
Amorphous silicQ
~ 10-1
:=
Sit OH}t,
c
o
-
~
'-
c
OJ
w
C
o
105
\...J
t,-
10- 9 Si 4Os IOH)4
5 6 7 8 pH 9 10 11 12 13 14
Figure 9. Solubility of amorphous silica as a function of pH
polymerisation
silicic acid + polyilicate ions ++polysilicic acid
+
depolymerisation
aggregation
+ colloidal silica (sol) + gel
+ +
(54)
deaggregation
Siloxane bonds are formed during the polymerisation and a
possible way of representing this is
OH OH OH OH
I I I I
Oll-Si-OH + Oll-Si-OH HO-Si-O-Si-OH (55)
I I I I
OH OH OH OH
: ea 2+ - 0 - SiO(OH)3
surf (56)
30
ro
......
)(
. .e.
. . . . . . 20 a
VI
1M
o
e
456 7 8 9 10 11 12
pH
CD
o
20
-
)(
e
N
VI
QJ
~
"0-
QJ
10
....
.0
~
"8 o
SiOz!NazO
[J 1· 00: 1
o 2·07:1
II 3·41:1
B 9 pH 10 11 12
Figure 11. Adsorption of silica by calcite as a function of pH
5 Initial SiO 2 M
GO Siod Na 20
0
~
0 1·00: 1 4·9 x 10"4
x
"'e 4
...........
VI
C1I
<5
e 3
"0
C1I
.D
L-
0
VI
"0
2
c:I
c:I
u
Vl
o
°3~~4~S~~6~7~~8~~9~10~1~1~12~
pH
Figure 12. Adsorption of silica by barite as a function of pH
Hanna [61] showed that starch depressed the fatty acid flotation
of calcite and barite, although the greatest starch adsorption
occurred on fluorite. Somasundaran [7,62] showed that starch
produced a more negative zeta potential on calcite and this was
interpreted to indicate that the weakly negative starch molecules
were adsorbed on cationic calcium sites. A similar
272
'"i"_ 700
CI
PYRITE
E 600
....
0
GALENA
+-
u 500
-
CIJ
0
u
400
0
c: 300
0
:.:: CHALCOPYRITE
....0 200
+-
c:
CIJ
u
c:
0
100
w
O2
3 4 5 6 7 8 9 11
pH
Figure 13.Effect of diethyl dithiphosphate concentration on the
critical pH values of pyrite, galena and chalcopyrite
[66]
Activation of sphalerite
Modification by pH
120
"j"
-100
C'I
E Marcasite
c:
0
:.= 80 14
0 hal copyrite
.-
L..
c:
cu
u
c:
0
60
u
cu
:E
c:
.0
40
>.
u
E
::l
'0 20
0
Vl
7 8 9 14
pH
ZnS + Cu 2+ + CuS + Zn 2+
surf (58)
feldspar +
beryl float
ca\ciwn hypochlorite
thicken
and
repulp
feldspar
CaF, float
frother
thicken
and
PbS float repulp
quebracho
alkyl sulppate
Na2C03
galena
sphalerite
chalcopyrite
pyrite I silicates
Pb andCu
sulphides float
S02
sodium dichromate
xanthate
pyrite I silicates
PbS
REFERENCES
39. Her, R.K., The chemistry of silica, J.Wiley and Sons, New
York, 1979.
49. Iwasaki, I., and Lai. R.W •• Starches and starch products as
depressants in soap flotation of activated silica from iron
ores. Trans.A.I.M.E. 364-371, 1965.
G.Barbery
FLOTATION MACHINES
Power number
Reynolds number
Np = C1
I
v (2)
(3)
I
ac 2
==-- I [C(x) - On] dx
s
cm2 V
C2
m
(4)
1 1 D 3 D NP D 2 (5)
Nm == 6 MxN
0.1 {(-) NQL + 0.21 - - } [l-exp-13(-) ]
L L 1NQL L
For the figures given for an impeller similar to the ones used in
some flotation cells the following value is obtained, for a cell
aspect ratio of 0.308 and the figures already given for Np and
NQL
N == 62
m
N D = ~ oLGg ) (A + B l!.)
o p D (6)
3
... =
'I' 0.075 [ ll(NL- No)02 ] • [ -ea 4 ]1/4
a LG gll (7)
D 4.38 0.115
NFr 1.96 D/L U (8)
192 ~L~ NRe QA
where PAlp 0 is the ratio of power drawn in the presence and in
the absence of aeration. Extensive data for laboratory flotation
machines have been measured by Arbiter and Harris and their
coworkers at Columbia University (see Harris [42,44] as well as
elswhere. For industrial machines, valuable information' for self
300
QA a D2 • 4 In N (9a)
P a D3 • 7 N1 • 8 (9b)
In N - om (D) (lOa)
(ll)
En d 3
i i
(12)
N-N
[1.2 + 260 ~ _ _ 0 D
(13)
°LG
for (N - N ) D
o
1.5 mls
Harris [44] has especially insisted on the importance of frother
addition on the control of bubble size in this sort of system.
Predicted bubble sizes according to these formulas are the
following for D/L = 0.25, D = 0.6m, oLG = 0.05H/m (to take into
account the effect of frother on lowering surface tension) N =93
tlmin for a turbine impeller and 74 tlmin for paddles). No~mal
flotation impellers of this size run at about 200 t/min. Thus $ =
13.55%, from Van Dierendonck's formula, a good average number for
a flotation cell and ds~ = 0.333 mm, also a reasonable predictive
figure. This example shows the value of multiple correlation
formulas based on dimensionless numbers.
_2/3
N = K D d 1/3
c P (14)
Oyama and Endo [30] have put forwards the following correlation
for vaned disk turbines under fully baffled conditions:
2/3 1 3
£
gi .(p s - Pi)
C
16Pi (15)
P P
s
Pw = Pw (16)
where Pw and Pw are the -power consumed with solids present and
absent respectively, and P is the average specific gravity of the
slurry, and Pw is water specific gravity.
p P*
s
Pw = Pw (17)
where p* is the average slurry specific gravity around
303
p* k (p - p )
w
+ pw (18)
p
a
p
NQ
~--------------------~----~ a
Figure 2 - Typical relationship between Pa/p power consumed in
the presence of air flow number Nq and without air,
in the presence of solid particles, as given by
Arbiter et al [38,43] NQ Earticles; common values in
laboratory cells are 2-4a~0 2.
EC a Nc Qab (19)
are presented with b=0.235 for the tin ore and b=0.05 for the
potash ore.
305
/
Shan
--. Denver
Aker Prooeller Booth D-R
Wedag
Air port
Shan
-Slandploe
()f~ser
1~"Y- hood
_ v v - Oi~se.
Rotatlon/, .00. ~
~... . . . Sala
:=''::ay)~~-=
OK Wemco
I'
,I
,/
"
"
I !I • !I,I
, II '
J
~.l ,I
I :
l.
--·1~!;-~·l.L1t-1-~;'1.-- 11:,
u.. _:li;M~~J ._U
Agilalr Weda9 BCS
I/
/
/
I ! :
•I
I
I
• I
":~~;~~~~;;i->'>
PTJ-h"rrp
•..t._ .LLu.. J ,.. ... __ .. ______ ..L. __ .,
r---· I
OK Type U Sala Wem.::o
h height
1 width
L length
D impeller diameter
C clearance of impeller above cell bottom
Volume .. V = hlL
Froth area = A - lL
D
Impeller aspect ratio R =-
L
Impeller clearance ratio C =~
D
Geometrically similar machines would lead to relationships of the
type
NQa a Df f - a
a 1
Under these conditions, Froude number varies as D2 - whic~+is
nil for a = 0.5. Reynolds number is then proportional to D •
However, for a 100 fold increase in cell volume, Reynolds number
would increase 4-9 fold, in a range around 5 x 10 5 , which
characterizes high turbulence; variations in this range are not
too significant.
311
E = ~ ; P a N3D5(N D2)-C
V a Dn (1 - r)
Reynolds' number
(21)
1
s
E
V (22)
~I
......
~Irl-------------------------------- N
'
5~~
CD
...... Ci(.~.~~..~:.•
............................
0·5]
The upper size limit for flotation to take place has been the
object of many investigations. In the absence of turbulence. this
size can be defined for an indefinitely extended surface area -
i.e. for a particle attached to an air bubble of finite diameter,
in which case capillary pressure can become a significant factor
for bubble diameters below O.5mm, and for particle size at which
self buoyancy can be obtained by the air bubble/particle
aggregate at a given bubble diameter. Schulze [19] has recently
given a complete analysis of the forces acting at the three-phase
interface, and conditions for stability. depending. for spherical
particles and bubbles, on particle and bubble diameters, contact
angle value, surface tension at the air-water interface, and
solid specific gravity.
1000
2
500
100
50
10 50 100 contact
'"
Figure 6 - Maximum particle size flotable
1. Static condition, plane interface. angle 0
(26)
FLOTATION KINETICS
(27)
Two major schools working in this field have been active in South
318
The NIM group around King has developed a kinetic model which
classifies particles in size fractions (D classes) and mineral
content fraction (G classes). As far as the particles are
concerned, each G class is assumed to have a characteristic
distribution of k values which must be determined from a
flotation experiment. Variations of this rate constant with size
has been taken as [108]
Ito
cP (d) = 2.33
a d 1.5
- (1-(-)
fj.
a
) exp - (-)
2
d
(28)
a = 0.5 d 2
max
where' d is the size at which one observed maximum relative
recover~~e model specifically takes into account variation of
the rate constant as a function of aeration by making it
proportional to the average bubble surface area:
A (29)
f3 (30)
S AV= 1
1= exp
f3
V
where f3=WKf; W is the mass of solids in the cell,
and K = H/d k cp (d) all particles
(31)
dC
E-) .. - k CF C
(32)
dt e W
Feed Tailings
from to
previous next cell
cell
Agitated V
siurry t ' Mt' Ct
F eed Tailings
....r "'"
r
Q0' C 0 Qt' C t
ba + 1 a (33)
y (k)
r (a+I)
k exp ( - b k)
dC (34)
-= - k C
dt
c eo exp (- k t) (35)
If particles doe not have all the same k, but have a distribution
according to f (k), then
00
Kapur and Mehrotra (96] have noticed, after a few other workers
(notably Harris and Chakravarti (89] that obtaining f (k) from
ele corresponds to an inversion of a Laplace transform, which
canobe done numerically, and they have presented results on this
line. The experimental data is usually not good enough to
calculate f (k) with a high precision.
Mass balances for pulp volume and froth volume are respectively
(37)
(38)
At steady state
(39)
dM t (40)
Qo C0 - k Mt - Qt Ct
dt
at steady state
Qf Mf (41)
k
Vf Mt
so that
k
k u (42)
l+k 1i.
d Qf
(43)
C ... C
0 J exp - k t f (k) d k
0 (45)
a + 1 GO
(47)
C = C (---E-)a+l
0 b+t
which explains the use which has been made of this function.
In plug flow reactors, all elements have the same residence time,
e. In perfect mixers, residence time distribution is:
(49)
calling e = _V_
qt
at steady state:
qoc o - qtCt (1+ke)
Recovery of k species .. --
qfc f
qoc o
ke
l+kB
(50)
1
then Recovery .. 1 - (l+ke)n
1 (52)
R .. 1 - --"':k---:n
(l +-.ne)
n
R - 1 - exp - (k n e) (53)
FLOTATION CIRCUITS
e [ (......L.)1/n]/ In ~) (54)
--=
T 1-R 1-R
then
n 1 2 5 10 15
e min 95.13 17.38 4.11 1.75 1.11
n a min 95.13 34.77 20.54 17.48 16.60
,.
a) Simple one product circuit :
number of cleaner banks can be
large (e.g. 6 - 8 for some ores
presenting selectivity problems).
EI +F s:: Feed
&6f
Ii) Ol c Conce ntrate
...... Ol
.
.-.
...... 0-
~c or Tailing s
NP> (Jonce ntrate
W ...... Tailin gs
......... P> Flowra te Feed
::I oc= 'aQ f
>0 Q, 0 ... =11-flaO~
~fi) Volum etric Im3 /min'
P> flowra te (1 - f~'(1 - xIs '~(l-xls
'tl + Qf + Qf'-
I"t P> Pg
It)
"1 Pg
~O
~ xSO( nk. (1-alk
...,::1 XS( a- + - - 1-a) 0" Qf
J
"1 ~ +- - .
+ - - - + - -k, -
P. 1 + k,O 1+ D
o P. 1 + k.8 1 + /e,0
EI P>
fa QI'-
~..., Im3 /minl aQr- (1-"aQ "
"1 ......
Water
0- 0 fIJ11 - x, 5 Q" ®
it/minI (1 - xis Q~ 11- fj'J)(l-x 'sQ" G>
III I"t Gangue
"1 p>
'< I"t 1 k.D
Low rate CV - - x a sQ:F ®
it/minI xa 5 Qf --Oxa sQ." 1 + k,O
~O
.-.'"'" cOfi~tant 1 + k,
W::l SO S
o k,O
High rate 1 . (3)
ofi)
--xI1- a'sO. O' --x(1 -a'sO .(- ®
...... c03sta nt it/minI x(l-a's QF 1 + k,O
...... 1 + k,1I
soli 8
it/minI sQr- <!J+<?;>+@ @)+@1-@
~ Solids
Ol
t-'.
::I
(JQ
t""
'<
::I
o
::r
329
, . . . . - - - - - - - 0 -I
o
~ O~I
-I . . . . . . 0
01-------.....::0 1
b) B configuration c ) A configuration
matrix matrix
(l+k 6)m -k 6 m -k 6 -k 6 m -k
s 1 stl s 7 st7 s 8 s 9 st9 s6l0mstlO-mst12=fs
-k 6 m -k 6 m -k 6 m -k 6 m -k
s 1 stl s 2 st2 s 3 st3 s 4 st4 s65mst5-ksu6mst6
+ (1+ks6l1)mstll = 0
d ikj = b ik + a ik k j 8 i (56)
O . • m.=F. (57)
=J =tJ =J
representing for each species N simultaneous linear equations.
The overall system is, of course, non linear since 6i is a
function of ~tj. An example of flotation circuit as well as the
derived configuration matrices is given in Figure 9. The
resulting mass balance equations are given in Table 3. As roughly
sketched above in the simple example given, an iterative
procedure is required to get the value of all flows at
convergence.
Testing of the simulator has been made for pilot plant runs at
the University of Natal, as well as simulation of industrial
flotation circuits. The value of such a programm for testing
modifications in circuit modifications has been presented by King
[110]. Figures 10 and 11 give an idea of the quality of
saimulation and of the interest in using the simulator for
outlining optimal configurations. Problems lie in data
acquisition, in a limited capacity to model froth behaviour and
to take into account predicted water flowrates.
VJ
VJ
""'"
60
2 6 10 II 12
CELL NUMBER
Figure 10 - N.i.m. simulator. Demonstration of its validity in
modelling industrial flotation circuit.
From King.
~Toillno.
10ko/a 1 .~"".'
~-:==-=--:--==-:-=~- 6lccj/s ~ Thl. configurollon produces
60. I ~ Ihls grade recovery curve
15kO/s 10110 • "
I\,
1I.
6 kO/s ,
~:.. 211 /s
o:!!. \ 0 Plont feed rates normally
ThiS confiIJurolion produces , ronlJl! from 1.5 10 4 kO/s
0:
w this grade recovery curve \ (510 13.5 lon/h)
Q.
Concentrate J \
&
u \
\
...J 'OI'~-p-'!I11'" , \
g
f- Feed 0.5k9/5
40'~------------~------------~------------~-
84 89 94 99
RECOVERY. %
From King.
w
W
IJ1
336
CONCLUSION
REFERENCES
12. Taggart A.F. Handbook of Mineral Dressing. 2nd ed. Wiley, New
York, 1945.
338
13. Anfruns J.P. and Kitchener J.A. The absolute rate of capture
of single particles by single bubbles. Flotation Fuerstenau
M.C. ed, AIME, New York, vol.2, 625, 1976.
Mixing
34. Arbiter N., Marris C.C. and Steininger J., Power requirements
in multiphase mixing, Trans AIME, 229, p.70, 1964.
36. Harris C.C. and Lepetic V., Flotation cell deSign, Mining
Engineering, 167, p.67, 1966.
37. Arbiter N., Harris C.C. and Yap R., A hydrodynamic approach
to flotation scale-up, 8th Mineral Processing Congress,
Leningrad, Preprint D-19, 1968.
39. Arbiter N. and Harris C.C. Impeller speed and air rate in the
optimization and scale-up of flotation machinery, Trans AIME,
244, p.11s, 1969.
40. Harris C.C. and Raja A., Flotation machine impeller 5peed and
air rate as scale-up criteria,Trans I.M.M.,79,p.C29s, 1970.
340
41. Harris C. C., How much flotation research really pays off,
Mining Magazine, 126, p439, 1972.
43. Arbiter N., Harris C.C. and Yap R., The air flow number in
flotation machine scale-up, Inst.J.of Min.Proc., 3, p.257,
1976.
Wemco
46. Reck W.H. and Kind P., New concepts in a large scale
flotation machine, Rudy, Prague, p. 134, 1970
47. Cus tred U. K., Degner V. R. and Long E. W., Recent advances in
Course Particle recovery utilizing large capacity flotation
machines, Trans AIME, 258, p.324, 1975.
48. Degner V.R. and Treveek H.B., Large flotation cell design and
development, Flotation, Fuerstenau M.C. ed., AlME, New York,
vol.2, p.816, 1976.
Denver
Aker
55. Sidery D., Sydvaranger's New Mill, Min.Mag., 146 (1), 1982.
Outokumpu Oy
Humbold - Wedag
Agitair
59. Spada M., Flotation Cell Agitair No.120, Revue Ind. Minerale,
52, p.179, 1970.
342
Sala
Minemet
Flotation Column
Flotaire
Davcra
Maxwell
Others
Flotation Kinetics-general
91. Huber Panu I., Ene Danalache and Cojocariu D.G. Mathematical
models of batch and continuous flotation, in Flotation,
Feurstenau M.C., ed., AlME New York, p 675, 1976.
92. Mehrotra S.P. and Kapur P.C. The effect of aeration rate
particle size and pulp density on the flotation rate
distributions. Powder Tech. 9. p213, 1974.
93. Mehrotra S.P. and Kapur P.C. The effect of particle size and
feed rate on the flotation rate distribution in a continous
cell. Int.J.Min.Proc. 2, p.lS, 1974.
95. Mehrotra S.P. and Kapur P.C. Optimal suboptimal synthesis and
design of flotation circuits.Sep.Science 9 (3),p.1967, 1974.
346
97. Harris C.C. and Rimmer H.W.Study of a two phase model of the
flotation process. Tr.ans.I.M.M. 75, C.153,1966.
.121 T.horne - G.C •. , Manlapig E.V.~ Hall J.S. and Lynch A.J.
Modelling of industrj,al. sulphide flotation circuits, in
Flo.tat:ion, .. Fuer.stenau M.. C. ed. AIME, New York, p. 725, 1976.
T.Zabel
INTRODUCTORY REMARKS
Dispersed-air flotation
Electrolytic flotation
Electrodes Clarified
Water
Effluent
Dissolved-air flotation
1. Vacuum flotation
2. Micro-flotation
3. Pressure flotation
it is a batch process
Cllrifiod
.ffluont
Floa:uloting
agent
(if requir1ldl
Sludge
CI.rified
Iffluont
Floa:ulating
ogent
(if requintdl
SaturltOf
Sludge
Clarified
effluent
Flocculating
agent
(if required)
For the removal of fragile flocs, for ins tance those produced
during potable water treatment, recycle-flow pressure flotation
is the most appropriate sytem. In this process the influent flows
directly to the flocculation tank or to the flotation tank if
separate flocculation is not required. Part of the clarified
effluent is recycled, pressurised and saturated with air. The
pressurised recycle water is introduced to the flotation tank
through a pressure release device and mixed with the flocculated
water. In the pressure release device the pressure is reduced to
atmospheric pressure releasing the air in the form of fine
bubbles suitable for flotation (20 to 100 11m in diameter). The
air bubbles attach themselves to the flocs and float to the
surface. The float can be removed from the surface and the
clarified water is taken from the bottom of the flotation tank.
Because of the additonal flow through the flotation tank due to
the recycle the flotation tank has to be designed larger than for
the full-flow sustem especially if the recycle flow required is
large, as for sludge thickening.
356
The raw water entering the plant is dosed with the coagulation
chemicals either in specially designed flash mixers or directly
in the raw water feed pipe. The coagulated water is subsequently
flocculated by gently agitation in the flocculator. The
flocculated water is mixed in the flotation tank with the recycle
stream containing the fine air bubbles. The bubbles attach
themselves to the flocs and the bubble/floc agglomerates rise to
the surface of the flotation tank and are removed as floated
sludge either by flooding or mechanical scraping. Part of the
flotation treated water is recycled, pressurised and saturated
with air in a saturator. The saturated water is returned to the
flotation tank through special pressure release devices in which
the pressure is reduced to atmospheric pressure precipitating the
air in the form of fine bubbles suitable for flotation.
Coagulation
Sludge
beach Recycle
Raw In-line Sludge
Water
level
control
1.2 1.2
51.0
...
I-
~
.\
., 1.0
...
Ii
~
~
§ 0.8 ,, oS
!z
,,
0.8
<II
II:
:::>
S
l- isc(
\\
II:
W
~ 0.6 ~ 0.6 8
...J
;: \ c(
o \ :::>
w \ o
~ \ iii
~ 0.4 \ 0.4 ~
\
I- \
z
o
~I-
','. . ___ .----_____C-.
0.2 • 0.2
9...
o 2 4 6 8 o
DISTANCE SEPARATING DOSING POSITIONS (m)
Flocculation
Figure 6 shows the effect of varying the paddle speed and the
corresponding mean velocity gradient G on the treated water
quality,which indicates that the optimum velocity gradient is
about G = 70 s -1. This was independent of the type of water
treated [7].
360
Tracer tests [B] using a slug dose of lithium chloride have shown
that the presence of the air bubbles improves the hydraulic
characteristics of the flotation tank, Figure.B.
361
3
~
IL
>-
~ Raw water: Turbidity 1.5 - 1.7 FTU
o Turbidity
o o Residual coagulant pH 8.9
III
a: Coagulant dose: 5 mgtl AI
:::l
f-
a: 1.4
w z
f-
« a
i=
~
o 1.2 0.6 «
-'
w :::l
~ \!l
«
~ 1.0 0.4 a
~ u
z -'
«
g 0.8 0.2 :::l
0
~ in
w
a a:
it 0.6 .1....-~---T'""---r---I---.,..~
8 10
UNIFORM PADDLE SPEEDS (rev/min)
32 50 70 92 118
MEAN VELOCITY GRADIENT GIs-I,
FLOCCULATION TIME
o. • Hydraulic 4.6 min at 8.2 m'lh
.. Hydraulic 5.7 min at 8.2 m' fh o
o Mechanical 10 min at 8.2 ml/h
:;
~ O.
>-
o
~
iii
II:
::>
----
~ 0.7
II:
w
!;(
. _.
~
C
w
!;(
w
0.6
~
.
II:
.-----
~
0.5.l,..--------r--------r---------,
4 6 8 10
FLOW RATE (m'fh)
CICo
2-5
to = .volume of tank
l··
J!I, flowrate
~I ~\
I
I
~
\
--<i)- no recycle
--I!I-- with 8% recycle
I \
1·0
!
I
~~
\
If! \
I \
0-5 I ~
I ,
, 't§I.
,
~
o +-~~§4~------~-----'-------T--~---r---=~~3_0
0-5 1-0 1-5 2·0 2-5
~
tlto
into the sludge collection trough. This method has low equipment
cost and the sludge removal has little effect on the treated
water quality. However, the sludge produced has also a very low
solids content (less than 0.2%) and the water wastage is
relatively high (about 2% of plant throughout) thus one of the
advantages of flotation, the production of thick sludge is lost
with this method.
As the sludge is scraped off over the beach fresh sludge from the
flotation tank surface is drawn by natural flow towards the beach
area. This type of scraping devices reduces the likelihood of
sludge break-up and. its associated deterioration in treated water
quality as the blades themselves create very little disturbance
i f the sludge layer on top of the flotation tank. It is worth
noticing that in potable water treatment the production of good
water quality is of prime importance whereas the production of a
thick sludge is only of secondary benefit. Best treated water
quality and sludge thickness are produced by operating the sludge
beach scraper continuously and by maintaining a sludge layer of
approximately 10mm on the flotation tank surface. It is also
important that the water level in the flotation tank is adjusted
correctly to avoid excess water being carried over the beach
during the sludge removal.
A full length scraper removes during each passage the sludge from
the whole surface of the flotation tank. It is important to
select the correct scraper speed and frequency of scraping. If
the speed is too fast it can lead to sludge break-up and to high
carry-over of water producing a thin sludge. If the speed is too
low or if the sludge is removed too infrequently, e.g. the
accumulated sludge layer is too thick, this can also lead to
sludge break-up during the removal resulting in a deterioration
in treated water quality. Least disturbance of the sludge layer
is peoduced by operating the scraper continuously at a scraper
364
.
.
Cl'
bJ)
.,-1
11<
365
Liquidl.ir =-=:=::;'\
i(;"
Air
Recycle Recycle
pump Liquid out· pump Liquid out-
to flotation unit to flotation unit
1--____--..---A_Electrode
Reaeration
pump suction pump discharge
Air in
- Air out
v.lve
Air air
discharge
Recycle
I
pump Outlet· to flotation unit Outlet· to flotation unit
100
'"
0 Water temperature 12.SOC
loading 1900 m1/m l Iday
'"
! Packing:
z 60
0
;:: Plastic pall rings
"'">-
::>
40
Plate distributor
Pressure 415 kPa
;1j
20
0
0 0.2 OA 0.6 0.8 1.0 1.2
PACKING OEPTH (m)
Extensive work [9] has been carried out on optimising the design
of a packed saturator. Different types of packing material were
investigated which indicated that the choice of the packing
material was not very important, by marginally better results
were achieved using polypropylene Pall rings which was also the
367
Different devices are being used for precipitating the air from
the saturated water. These include proprietary nozzles, needle
valves and simple gate vaives. It is important that the pressure
is released close to the flocculated water stream to minimise the
coalescence of the bubbles resulting in a loss of air bubbles
available for flotation. Good mixing of the air bubbles with the
flocculated water stream is also essential to facilitate
bubble/floc contact. To achieve effective air release the
pressure should be reduced suddenly and highly turbulent
conditions must exist in the air release device. However, the
velocity of the recycle stream leaving the device should be low
enough to minimise floc break-up.
160
140
;::: 120
'"E
o
w
~ 100
w
...J
W
cr:
ow 80
>
...J
oen
5 60
cr:
C(
40 Air atmosphere in saturator
Nitrogen-rich atmosphere in saturator
20 Temperature values in °c
5')
., ,, ,I \
it:
I \
\ -@- Needle Valve
I ,
,
I \
\
--@-- WRC Nozzle
I
I
j 25 I
20
,
I
I
,
I
I
15 I
I
10
I
I
\
\
,
~ "-
5 I
I
'ls.,
I
I
's_
o~~~~--~----~--~~~~~~~
o 20 40 60 80 100 120 140 160 180 200
Bubble diameter ll'm) •
Figure 13. Bubble size distribution produced by needle valve and
WRC nozzle [8]
4·0
3·0
~r2'0
:2 1·0
.c
~
4·0 5'0 6·0 7·0 8·0
•
9·0 10·0 11·0 12·0
Aphanizomanon Microcystis
200
102000
100
150
E
"! "
i
!.l!! ~'" "f
"1ii" .l!!
:;::
c "!
.
'i c
... ~'" ~"
'i .2 0
.;:;
"'u
"'u 100 .="
'S! c ...
'0
50
:j
"'. '.,"
C 1: c c
.. ".
.2 .2
)( .;0 ,~
,S "E 1ii 1ii
c
au ~ 1::>
0
",
..
~
!! "5l .."
'6
~ ~
u
'iii 50 'iii
!P
~ c(
2800
0 0
.. Chlorinated
ferrous 48000 3.6
sulphate
100
~
;i90
1)
~
~BO
...J
..:
";i 70
o 1.0 2.0 3.0 4.0 5.0 6.0 mgt) AI
o 2.0 4.0 6.0 8.0 10.0 12.0 mw'1 Fe
COAGULANT DOSE
The sludge produced from this type of water was more like a paste
and tended to grow into the water similar to an iceberg rather
than float on the water surface. The sludge started to break-up
after only 30 minutes accumulation at the surface. The best
method for the removal of this sludge was continuous scrap'ing
373
COST OF FLOTATION
where the Captial Cost is in f1000 and the Area is the area of
the flotation tank alone, in m2 • Costs do not include any
substantial buildings which might be needed to protect the
flotation plant from adverse weather. However, flocculation and
saturation equipment are included in the costs.
Improved flotation treated water quality similar to that achieved with sedimentation was obtained
by increasing the flocculation time from 12 to 16 min.
375
(b) Mechanicals of £160 000 for all mechanical plant for flash
mixing, flocculation, flotation, chemical mixing and dosing,
manual control and nominal coverage of the flotation tanks.
Note these costs are exclusive of raw water and high lift pumps,
sludge disposal facilities and all buildings.
REFERENCES
12. Zabel, T.F., and Hyde, R.A. Factors influencing dissolved air
flotation as applied to water clarification. Paper 8 Papers
and Proceedings of the Water Research Conference on Flotation
for Water and Waste Treatment. Medmenham, England, May 1977.
14. Cost information for water supply and sewage disposal. WRC
Technical Report TR6l, Water Research Centre, Medmenham,
1978.
WASTEWATER TREATMENT
Hermann H.Hahn
Universitat Fridericiana,
75, Karlsruhe, FRG.
INTRODUCTION
iI
UPWARD MOVEMENT OF
SUBSTANCES SPECIFICLY FLOTATION OF DISSOLVED
LIGHTER THAN WATER SOLIDS WITH COLLECTORS
( FLOTATION ) PRECIPI- II ION
TATION I I FLOTATION
FLOTATION i i
FLOTATION OF SUSPENDED
SOLIDS WITH COAGULANTS
FLOTATION OF
SUSPENDED SOLIDS
Figure 1: Flotation - Definition of the process as understood in
this discussion
381
T5
14 000
II
I I
II
I
!l~
d:
!I I
~------------------~C>
TIME
D
SWF
~ 106 (TO/YEAR)
~106 $
PROG - PROG - STAllS - PROG -
NOSIS NOSIS TICS NOSIS
AC/DC CONVERSION
COMPRESSED-AIR-FLOTATION ELECTRO - FLOTATION
RECYCLE
Depending upon the point of view one can identify a very large
number of reaction steps of more physical or more chemical nature
or one will find that only relatively few significantly differing
steps are of importance for the technical operation of a
flotation unit.
+ STEP 1: ~
AIR BUBBLE FORMATION
( PRESSURE DIFFERENCE, NOZZLE TYPE,
FLUX, W,W,CHARACTERISTICS )
STEP 2:
I AIR - SOLIDS AGGREGATION
( NUMBER CONCENTRATION, VELOCITY
I GRADIENT, SOLIDS FORM, AIR -
I WATER - SOLIDS CHARACTERISTICS )
I
I
1
STEP 3:
I UPWARD MOVEMENT/REMOVAL
( AIR - SOLIDS RATIO, SOLIDS DENSITY
I REACTOR FLOW RATE, DETENTION TIME
I DISTRIBUTION )
I I
L _ JREATED SEPERATED
•
WASTE WATER SOLIDS
+
Figure 5: Schematic view of most significant three reaction steps
in waste water flotation, indicating crucial design and
operation parameters.
160
NOZZLE TYPE 1
140
:e::
~
......
:::I
120 ~
LL.I
I-
LL.I
100
~
.....
c:::I
LL.I
-.J
c:o
10 c:o
:::I
c:o
LL.I
C.!)
60 -=l:
~
LL.I
~ )(
'0
GAS PHASE
SOLID PHASE
E
S,gADHESiON
= 6"t + 6
l,g
- 6
S,g
(1)
= 6.,t + 6t
,9
• COS e ( 2)
0,05
20 40 60 80 m 120 140
>-
--
u
z:
UJ
U
u..
u..
UJ
-.J
:;;
o
:E
UJ
0::
-
V>
~
-l
o
V>
REACTOR REACTOR
INFLOW OUT LED
r
/
HORIZONTAL FLOW /
VELOCITY (REACTOR FLUX)
VELOCITY OF
UPWARD ~
110VEMENT 0 ......
./
W
/'
4-- TRAJECTORY OF LEAST FAVORABLY
FLOC WITH 0 / REMOVED AIR - SOLID - COMPLEX
~---------------------------------------~
LARGEST FLOATING DISTANCE,
-~ VF
F
L.LJ
en
<C
L.LJ
ffilO
Q
:z:
-
<C
.....J
will also affect in their way the flow-through pattern. Even the
395
L L
HYDR. SURFACE LOADING Q (M3/M2 ·H)
16~-------------------.
1S
14 T
13
12
11
10
-+-+
9- LZ
TYPE 1
8
7
6
S
4
3
2
Examples of Application
-
... 1
..
SLU.DGE
(FLOATED+SETTLED)
QUANTITY
DRY SOLIDS CONTENT
lll.EUlli flOTATION REACTOR EFFLUENT
QUANTITY GEOMETRY,e SOLIDS CONCENTRATION
SOLIDS CONCENTR. HYDR. SURFACE LOADING 0iJ' OTHER SUBSTANCES
CHARACTERISTICS VE~OCITY OF FLOTATION OXYGEN-CONCENTRATION
OF: SOLID-PHASE SOLIDS SURFACE LOADING~
UQUID-PHAS AIR/SOLIDS - RATIO
Sludge: 0.5 m3 /h
dissolved oxygen = 1.9 mg/1
TS R::27.8 g/l
I =35.5 ml/g
sv
DeSign Criteria
b)For the aggregation of bubbles and solids and for the transport
of the bubble-solids-complex
Effective surface area including baffle arrangement
Effective reactor depth, sludge handling and storing
Inflow and outflow arrangement, determining flow-through
pattern
>-
o
--
0::: l
:z
r- CONSTRUCTION OF MODEL
e <c
I - I.!) (FR, RE, DEPTH, DETENTION TIME)
<C --
0::: I
<c en
c....w
UJ >- BATCH EXPERIMENTS ON
0:::2:
c....- VELOCITY
:E
o
W
REACTOR SURFACE
u..
e 0::::
I.!)
FROM DESIGN SURFACE LOADING
2:0
<..!) I-
-u
(I') <c
UJ w
00::::
REACTOR DEPTH
FROM AVERAGE DETENTION TIME
CONTROL OF A/S
( A/S RESP, QRECYCLE )
ADDITION OF CHEMICALS
( COAGULANTS, COLLECTORS, ETC, )
Experiments
HYDRAULIC
+
SOLIDS LOADING
i
SS
AH
Vfloat.--t - -
t
2- 1
I
PARAMETER REDUCTION EFFLUENT
(%) CONCENTRATION (MG/U
~.
~ SOLIDS , TURBIDITY , 40 - 60 0II'iji'
~l-.I
L L I - - - - - - ~- -
~ SETTLEABLE SOLIDS 95 - 100 - - - - - -- lLJ
0::
~ .WITHOUT COAGU LANTS
:::>
'iO~
d l SOLIDS 50 - 60 150 ~ c:r:
lJ.J
0:: 1--
I
-
::r; 0::
z WITH COAGULANTS (LIME) LL lLJ
lJ.J ::r;
o - 50
:£ I-
SOLIDS 85 - 95 ~ 0
I~
0::
I-
I SUSPENDED SOLIDS 90 10
u
0...
TOTAL PHOSPHOROUS CA.95 0.5 - LO
~
~'(H SCALE 'Af VAl UE
CANNERY, SU",,[j,DEO
~ SOLI DS IHESS
en lWiNICAL DAF,
rt AL.
lET (13)
!ll ADDITiUN OF IIL2(S04)3 BODS
~
rt
til .c-
11 0
-...J
"':1+**0"11>
~
"". II *II II II II "'0 "
ClO
11 II> n II> ~ ~
/I) :l II> :l "". "".
"". M "". M M
NOOOO"O"
O:l:l:l 0
" "".'0 ~
n"". n"". nOM
Mt"' ~
11 .... '0 '0 '0 '< '0 TYPE OF SLUDGE SOli liS COilTElH OF SLUDGE (%)
/l)MOOO/l)O I SOunCE
II>/I)~~~~~ 0 2 3 4 5 6 7 a
!
9
!
! .
MI1'<'<'</I)'<
S II> /I) /I) /I) n /I) a
/l)M~~~M~ PRIMARY SLUDGE
:l ~ /I) I'D I'D 11 I'D z b'
M 11 n n non 0 "/77///:/1
I IIILSON(lI1>
/l)MMM~M
11 11 11 '< 11 ~
fr°OOMO f-.:. PRIMARY SLUDGE HILSON
~~~/I)~
M'<'<'< '< z (14)
II> M M M M W
/I) I'D I'D /I) ~ a
PRIMARY SLUDGE CROWE AND
g~ 0 LOHNSON(5)
IJ.I 7777/7T
'0 M "". I/)
11 0"
0 PRIMARY SLUDGE MOGEUIICV,I
n M
I'D 0" (6)
fIl /I)
fIl
II> a JORDAIl Ali:)
I'D ~ ACTIVATED SLUUGE
ton~ SCIIERER <17)
ton "".
"". M
n "". a BRAITHWAITE
"". 0
/I) :l
ACTIVATED SLUDGE
:l Z
n 0 0
'<ton IBRA ITHWi\ ITE
i= ~ ACTIVATED SLUOG' (18)
"':I
"". /I)
:l
;:! 17·1» >»})-)?J 7 7 7 71
fIl (")
o -
~~ G: PRIMARY + ACTIVATED IETTElT
~w SLUDGE 0' . . . ·777
~-~~7'~ (19)
~
OQ
/I)
""7. ]
409
In the study that produced the cost function shown in Fig.21 and
22 both approaches have been used. The original cost functions
contain projected and actually occurred costs where the actually
expended finances were only slightly higher than those antic-
ipated.
sao
200
~ 100
o
50
o
o
:::J 20
~
en 10
8 5 • TOTAL
X HOUSING ETC.
+ SLUDGE SCRAPER ETC.
2 o COMPRESSOR AND PUMPS
......
SOO
200
®
~ 100
.::::I
SO
20
en
f-
en
o
10 • TOTAL
u
5 XENERGY
+ PERSONNEL
2 o MR
7
I
U)
~
U)
6 II
a 5
'1<90%
u '1< 85% '
--
'1< 80%
U 4 Sedimentation: 'I < 70%
U. 3
U 2
u.J
CL
U)
50 Ul ;!Xl 500 1000 2000
--
5
U '1<94%
4
l L. ~< 92%
3 '1< 90%
U
u.J 2 Sedimentation: ~< 85 %
CL
U)
50 100 200 500 1000 2000
---------------------------------------------------------y
FILTRATION
100,000 POP,EQ,
FLOTATION
10,000 POP,EQ,
10 20 30 40
I
50
I
60
It>
70
TOTAL SPECIFIC COSTS (10-2 DM/M3 WW)
REFERENCES
INDEX
amphiboles, 37
amphoteric site binding, 175
calcite, 242
capillary number, 94
capture mechanisms, 26
cations, polyvalent, 261
cell design, 313, 360
cell tank geometry, 308, 310
chelating agents, 251
circuits,
flotation, 325, 326-329
simulation, 329-336
coagulation, water treatment, 356
coarse particles,
detachment from bubbles, 205
maximum floatable size, 203, 205-207
collectors, 10, 391
adsorption mechanisms, 247
petroleum, 12
thio-, 10, 247, 252
structural formulae. 246
collision effeciency.
fine particles. 202
417
measurements, 198-203
single bubbles, 197
theory, 294
wastewater, 388
colour removal, 371
composition of particles, 291
contact angle, 8, 79
equilibrium, 86, 92
hysteresis, 8, 84
non-equilibrium, 92-94
wastewater, 390
continuously stirred tank reactors, 324
costs,
wastewater treatment, 405, 409-412
water treatment, 373
Coulombic attraction, 247
cyanide modifier, 276
cylindrical reactor, 398
phenomena, 321
rupture, 218
frothers, 233
Hallimond tube, 29
high energy surfaces, 95
hydrogen bonding, 25, 231
hydrophilic surfaces, 80, 92
hydrophobic association, 247
hydrophobic solids, 80, 86
effect on liquid films, 219
impeller geometry, 299, 307
induction time, 194, 198
intensity of turbulence, 297
interface,
atomistic description, III
experiments and theory, 181
mineral-water, 232
interfacial tersion, 80, 122
isolectric point (i.e.p), 184, 236
isotherms, adsorption, 97, 186
machines,
flotation 293, 305, 339-344
classification 306
Marangoni effect,84
mass balance around flotation cell, 328
mechanisms,
420
flotation reagents, 40
machines, 294
micas. 37
microflotation,352
minerals list, 12
mineral processing flowsheet, 229
mineral separation examples, 277-281
mineral types,
elemental. 33
non-ideal,44
oxides, 33
salt-type, 33
silicates, 33
sulphides, 33
mixing dynamics, 298
mixing reactors, 295
mixing in solid-air-water systems, 304
model experiments in wastewater, 403, 404
modifiers, 233, 256, 261, 263, 265, 275
molecular crystals, 245
oil collector, 9
oil flotation, 5
organic depressants, 43, 271
oxide-aqueous interface,
electrical double layer, 175-181
oxides, 33, 34, 41, 234
flotation, 255
solid system, 137-141
particle,
bubble collisions, 194-203
composition, 291
shape, 291
421
quartz, 239
anionic and cationic flotation,257
collection efficiency, 200
collision with bubbles. 194-203
induction time. 201
quebracho, 271,272
rate of flotation. 29
reactors,
flotation machines. 295
reagents.
mechanism, 40
residence time distribution. 323, 362
rest potentials of sulphide and ethyl xanthate. 254
reverse flotation. 18
site-binding,
amphoteric, 175, 189
size of particle,
maximum floatable, 203, 205-207, 314, 315
sludge scraping, 363
slurries, 303
soaps, 11, 43
sodium silicate modifier, 265-271
solid-air-water systems, 304, 392
solid-liquid interfaces,
state function, 124
solvent-surface interaction, 116
sphalerite, 7
spheres,
effect on froth drainage, 220
flotation, 199
starch modifier, 263, 271
stormwater treatment, 381
sulphide, 4, 5, 33, 40, 243, 272
surface active agents,
charge on bubbles, 69
effect on bubbles, 64
surface bonds, 114,
surface chemistry, 32
surface elasticity, 102
surface properties,
acid-base, 115
heterogeneity, 121
surface reactivity, III
surface tension gradients, 96
surface work, 122
tank design,
water treatment, 360
thermodynamic aspects, 22, 231
electrical double layer, 146-159
solid-liquid interface, 122, 126
temperature effects, 293, ·372
test cells for flotation, 222
tracer tests, 362
turbulence intensity, 297
Kolmogoroff, 300
theory, 300
ultra-flotation, 6
xanthates, 11
ethyl, 254
zeta potential, 24
quartz, 260
425
APPENDIX
THE SCIENTIFIC BASIS OF FLOTATION
DIRECTORS
ASSISTANTS
LECTURERS
PARTICIPANTS