International Journal of Mineral Processing, 23 (1988) 33-53 33

Elsevier Science Publishers B.V., Amsterdam m Printed in The Netherlands

Frot h St abi l i t y, Par t i c l e Ent r a i nme nt and
Dr a i na g e i n Fl ot at i on m A Re v i e w
T.V. SUBRAHMANYAM .1 and ERIC FORSSBERG
Division of Mineral Processing, Lule~t University of Technology, S-951 87 Lule~t (Sweden)
(Received September 11, 1986; accepted after revision March 27, 1987)
ABSTRACT
S u b r a h m a n y a m , T . V . a n d F o r s s b e r g , E . , 1 9 8 8 . F r o t h stability, p a r t i c l e e n t r a i n m e n t a n d d r a i n a g e
i n f l o t a t i o n - - a r e v i e w . I n t . J. M i n e r . P r o c e s s . , 2 3 : 3 3 - 5 3 .
T h e f r o t h a n d its stability, t h e e n t r a i n m e n t a n d t h e d r a i n a g e o f p a r t i c l e s i n f l o t a t i o n w e r e l o n g
b e f o r e r e c o g n i s e d a s i m p o r t a n t f a c t o r s w h i c h a f f e c t r e c o v e r y a n d g r a d e . A t o o s t a b l e f r o t h is dif-
ficult t o h a n d l e b u t , o n t h e o t h e r h a n d , a n u n s t a b l e f r o t h is l e a s t d e s i r a b l e . T h e r e f o r e , a f r o t h o f
c o r r e c t s t a b i l i t y is o f u t m o s t i m p o r t a n c e . H o w e v e r , t h e q u e s t i o n is w h e t h e r t h i s p h e n o m e n o n is
r e l a t e d t o t h e f r o t h i n g p r o p e r t i e s o f a f r o t h e r o r t o t h e p h y s i c a l , c h e m i c a l a n d g e o m e t r i c a l c o n d i -
t i o n s o f a s y s t e m ! T h e e n t r a i n m e n t a n d d r a i n a g e o f p a r t i c l e s i n f l o t a t i o n a r e c o n c e r n e d w i t h t h e
p u l p / f r o t h p h a s e s . T h e p r e s e n t p a p e r d e a l s w i t h t h e c u r r e n t a s p e c t s o n f r o t h stability, p a r t i c l e
e n t r a i n m e n t a n d d r a i n a g e , b a s e d o n a d e t a i l e d l i t e r a t u r e r e v i e w .
I N T R O D U C T I O N
T h e flotation process is k n o w n to b e g o v e r n e d b y a m u l t i t u d e of interacting
variables a n d it b e c o m e s necessary to h a v e a k n o w l e d g e of those that contrib-
ute to t h e final yield. I n a three-phase s y s t e m like f r o t h flotation involving
solid-liquid-gas, t h e efficiency o f separating t h e values f r o m t h e g a n g u e is con-
sidered to b e a function o f t h e a d h e r e n c e o f a n air b u b b l e to t h e required m i n -
eral particle. T h e role of t h e gas p h a s e in t h e f o r m o f dispersed b u b b l e s in a
p u l p is to carry t h e h y d r o p h o b i c m i n e r a l particles, o b t a i n e d as concentrate
a l o n g w i t h t h e froth f r o m t h e flotation cell. F r o m t h e v i e w point o f handling,
the froth t h u s collected s h o u l d die d o w n immediately. T h e froth p h a s e is i m -
p o r t a n t s i n c e it c a n affect t h e flotation recovery a n d grade. It is considered
that a small b u b b l e d closely knit froth is favourable for h i g h recoveries a n d a
loosely knit froth o f large b u b b l e s for g o o d grades. T h i s n e e d s to b e e x a m i n e d
in t e r m s o f particle e n t r a i n m e n t a n d drainage since all these p h e n o m e n a are
*1On leave from the departamento de Geologia, Laboratory of Mineral Processing, UFRN, 59.000
Natal-RN, Brazil.
0301-7516/88/$03. 50 1988 Elsevier Science Publishers B.V.
;]4
AIR CONCENTRAfF
(-measured rate of ~ecovery
ceLl
bul k T d r a L n a g e
t r anspor t ent ralnment and
by colLapse
bubbl es
A~R I FEED I TA/MNG
Fig. 1. Transport paths of materials in flotation (Flint, 1973).
J Finepo~tic,es J
I s i n " . . . . I 1 H g h I
Fig. 2. Schematic diagram showing the relationship between the physical and chemical properties
of fine particles and their behaviour in flotation. (G) and (R) refer to whether the phenomenon
affects grade and/or recovery (Fuerstenau et al., 1973).
i nt er r el at ed a nd i nf l uence t he r ecover y a nd grade, i.e. low grade at hi gh recov-
er y and vice versa. Figs. I a nd 2 i l l ust rat e t he mat er i al t r ans por t pat hs a nd t he
adver se effect s of t he pr es ence of fi ne par t i cl es i n fl ot at i on, respect i vel y.
A f l ot at i on pl ant oper at or is of t en baf f l ed wi t h t he pr obl em of choosi ng a
f r ot her for a gi ven ore-col l ect or syst em because of l ack of suf f i ci ent dat a on
f r ot her per f or mance. The sel ect i on of a f r ot her is most l y based on a t r i al - and-
er r or basis. A sur vey car r i ed out in di f f er ent f l ot at i on pl ant s r eveal s t ha t t he
most commonl y used f r ot her s are pi ne oil, cresyl i c acid, met hyt i sobut yl car bi -
nol and t r i et hoxybut ane ( Boot h a nd Fr eyber ger , 1962 ) ei t her i ndi vi dual l y or
in combi nat i on wi t h ot her f r ot her s. Tabl e I gives some i mpor t ant pr oper t i es of
t hese f r ot her s a nd some col l ect ors wi t h f r ot hi ng propert i es.
A consi der abl e numbe r of paper s have appear ed i n t he l i t er at ur e on f l ot at i on
TABLEI
Gener al f r o~i ngpr opor t i es of ~mecommon~us edf r ~he~andcol l ~t or s
3 5
T y p e N a m e G e n e r a l properties o f f r o t h Solubility
a t 2 5 C
g / 1 0 0 0 g
o f soln.
P r o d u c e d f r o m
R - O H Pine oil Small bubbles, closely knit 2.5
(cyclic alcohol type) structure, breaks down
readily
Cresylic acid Similar to pine oil but
(aromatic alcohol type) larger bubble size
1 . 6
(at 2 0 )
M e t h y l i s o b u t y l c a r b i n o l
(aliphatic alcohol )
R' O(RO)xH Polypropyleneglycols
( polyglycol type)
( R ' O ) x R T r i e t h o x y b u t a n e
( a l c o x y t y p e )
Larger in b u b b l e size, less
c o m p a c t structure; re-
quires large quantities t o
f o r m a close structured
froth
Compact, lasting froth complete/
structure; breaks down partial
readily
Resemble those of pine oil 8
froths (at 20 )
Closely textured stable
bubble aggregates, difficult
to disintegrate even by
water jets and sprays
RCOOH Fatty acids
RSO3Na Sulfonates
RNH2 Amine collectors
T u r p e n t i n e o r p i n e s t u m p
b y distillation o r s o l v e n t
extraction. Is a m i x t u r e o f
t e r p e n e alcohols, ketones,
e t h e r s a n d h y d r o c a r b o n s .
T h e a l c o h o l c o m p o n e n t s
a n d B terpineols, f e n c h y l
a l c o h o l a n d b o r n e o l a n d
c a m p h o r ( a k e t o n e ) a r e
t h e c h i e f frothing
c o m p o n e n t s .
B y p r o d u c t o f c o k i n g o f coal
a n d t h e r m a l c r a c k i n g o f
p e t r o l e u m . T h e p e t r o l e u m
cresylics a r e m o r e w i d e l y
u s e d t h a n t h o s e o b t a i n e d
f r o m coal.
P o l y p r o p y l e n e g l y c o l s o f
l o w m o l . w t . P r e p a r e d b y
reacting p r o p y l e n e o x i d e
w i t h p r o p y l e n e glycol.
S y n t h e t i c n o n - i o n i c
frother s h o w s l i m i t e d solu-
bility in w a t e r , readily
dispersible.
P e t r o l e u m
R e f i n i n g o f w h i t e oils a n d
sulfonation o f o t h e r h y d r o -
c a r b o n fractions.
frothers (Wrobel, 1952; Gaudin, 1957; Boot h and Freyberger, 1962; Kl assen
and Mokrousov, 1963; Harris, 1982; and Lovell, 1982 ) and any at t empt to deal
wi th the f undament al aspects of frothers will merely be a repetition. The role
of particle size i n fl otati on has been discussed by Gaudi n et al. (1931) and i n
detail reviewed by Trahar (1981). Hausen (1974) discussed t he types of froths
and related problems in fl otati on circuits and metallurgical plants.
36
The scope of t he pr esent paper is rest ri ct ed to t he rel at ed aspect s of frot h
stability, part i cl e ent r ai nment and drai nage in fl ot at i on and t he t opi cs are dis-
cussed as shown below;
Fr ot h st abi l i t y
- Fr ot h st abi l i t y meas ur ement
- I nf l uence of frot her
- Fr ot her i nt er act i on wi t h collectors
-Cl assi fi cat i on of frot hers
- Ef f ect of i nt er act i on pr oduct s on frot h
- Ef f ect of part i cl es
Part i cl e ent r ai nment
- Par t i cl e size - - fl ot at i on and e nt r a i nme nt
-Degree of ent r ai nment
- Li qui d l amel l a t hi ckness - - ent r ai nment
Drai nage
Summar y and concl usi ons
FROTH STABILITY
Fr ot h st abi l i t y me as ur e me nt
The st abi l i t y of a frot h is t he t i me of its persi st ence. Harri s (1982) referred
to t wo t ypes of frot hs - - unst abl e and met ast abl e. Unst abl e frot hs are t hose
whi ch cont i nuousl y break due t o dr ai ni ng of liquid from bet ween t he bubbl es
and met ast abl e frot hs can persi st for qui t e l onger t i mes in t he absence of dis-
t urbances. The quant i t at i ve pr oper t i es of a f r ot h depend upon a number of
variables. Sun (1952) i nvest i gat ed t he f r ot hi ng charact eri st i cs of pi ne oils and
expl ai ned t hat t he frot habi l i t y is governed by rat e and t i me of aerat i on, hei ght
of liquid col umn, chemi cal composi t i on of t he frot her, sol ut i on pH, t emper a-
t ur e and frot her concent r at i on in sol ut i on. Two met hods, i.e. compr essed air
f r ot hi ng and sucked air frot hi ng, were used t o measure t he frot h st abi l i t y in a
frot h met er. Li vshi t s and Dudenkov (1965) descri bed mechani cal and pneu-
mat i c met hods. I n t he f or mer a known vol ume of aqueous f r ot her sol ut i on
(general l y 25-100 ml ) is subj ect ed t o shaki ng in a glass cyl i nder for a given
t i me. The t i me of persi st ence of t he f r ot h aft er shaki ng is t he degree of f r ot h
stability. I n t he pneumat i c met hod, air was bl own i nt o t he aqueous f r ot her
sol ut i on t hr ough a por ous glass fi l t er at a cons t ant rat e and pressure. The
degree of dynami c st abi l i t y is mar ked by t he ma xi mum vol ume and t he char-
act eri st i c of st at i c st abi l i t y by its rat e of dest ruct i on.
For t hr ee- phase f r ot hs t he st abi l i t y is governed by a number of fact ors in-
cl udi ng part i cl e size, hydrophobi ci t y, etc. The st abi l i t y of a t hr ee- phase frot h
was measur ed by Di ppenar (1982) in a glass cyl i nder cont ai ni ng solids and
37
aqueous f r ot her sol ut i on. The f r ot h was pr oduced by agi t at i on and t he i mme-
di at e f r ot h vol ume was not ed. The met hod is si mi l ar t o t he one descri bed by
Li vshi t s and Dudenkov (1965).
The effect of solids on f r ot h st abi l i zat i on is measur ed in t er ms of f r ot h hei ght
or vol ume wi t h respect to t i me.
Influence of frother
A bubbl e pr oduced in wat er is unst abl e. One of t he prerequi si t es for a suc-
cessful fl ot at i on oper at i on is t he st abi l i t y of t he bubbl e- par t i cl e aggregate. A
st abl e bubbl e is pr oduced by usi ng a frot her, t he f unct i on of whi ch is t o de-
crease t he surface t ensi on of t he ai r - l i qui d i nt erface. The f r ot her mol ecul es
i mpar t st abi l i t y t o a bubbl e by mi gr at i ng from a regi on of low surface t ensi on
t o a hi gher value due t o t he surface t ensi on gradi ent . Wrobel (1951) measur ed
t he rat e of adsor pt i on of commonl y used frot hers at t he ai r - sol ut i on i nt erface
and f ound appreci abl e var i at i on in surface t ensi on wi t h t i me, i ndi cat i ng a low
rat e of mi gr at i on of mol ecul es wi t h aqueous sol ut i ons of pi ne oil and t ri et hox-
ybut ane. Wi t h sol ut i ons of i soamyl and met hyl alcohols equi l i bri um was
achi eved in a few seconds. Br own et al. (1953) and De Vries (1957) consi der ed
t he overall st abi l i t y of f r ot h t o be a f unct i on of t he bubbl e size.
The i nfl uence of f r ot her concent r at i on on bubbl e size was i nvest i gat ed by
Gr under et al. (1956) and Benet t et al. (1958). The bubbl e di amet er s observed
by t he m vari ed bet ween 0.2 and 0.7 mm for pi ne oil concent r at i ons of 10-20
mg/1 whi ch corresponds to concent r at i ons general l y used in practice. The ef-
fect of bubbl e size on t he rat e of fl ot at i on of fine part i cl es was i nvest i gat ed by
Ahmed and J ames on (1985). The mean bubbl e size vari ed bet ween 0.075 and
0.655 mm wi t h part i cl es less t ha n 50 mm and t hey concl ude t hat fine bubbl es
were superi or for t he f l ot at i on of fine particles. Thi s is due t o t he fact t hat fine
bubbl es behave like solid spheres and t ake up mor e l oad t ha n larger bubbles.
Recent l y Szat kowski and Freyberger {1985) observed t hat fine bubbles (10-100
/~m) wi t h t hei r l oad of quart z part i cl es were r esi st ent t o coalescence and t he
pr oduct i on of a st abl e f r ot h requi red mi neral i zat i on. Lapl ant e et al. (1983)
observed a lower f l ot at i on rat e in a syst em havi ng no f r ot her and at t r i but ed
t hi s t o an i ncrease in t he ai r flow rat e whi ch caused an increase in bubbl e
di amet er. I t was f ound t hat even a ppb concent r at i on of CsH13OH pr ol onged
t he t i me of coalescence of bubbl es ( Sagert et al., 1976).
Frother interaction with collectors
The f r ot her - col l ect or i nt er act i on in fl ot at i on was fi rst post ul at ed by J. H.
Chr i s t man in 1930 (see Lej a and Schul man, 1954). I t received bot h cont ra-
di ct i ng (Wark, 1938) and suppor t i ng ( Taggar t and Hassialis, 1946) views.
The t heor y gai ned gr ound onl y aft er t he work of Lej a and Schul man (1954)
who expl ai ned t he effect i veness of a f r ot her on i nt er act i on wi t h a collector.
38
Air
! t s
Fig. 3. Mechanism of bubble attachment: bubble approaching a collector coated solid surface:
diffused monolayers of associated and unassociated molecules at interfaces and in solution (Leja
and Schulman, 1954).
Air
Fig. 4. Mechanism of bubble attachment: adherence of an air bubble established through the
penetration of the monolayer at the solid/liquid interface by the monolayer at the air/liquid in-
terface (Leja and Schulman, 1954).
Wrobel (1951-52) discussed linear and lamellar theories for bubble-particle
adhesion. The linear theory states t hat the conditioned particles maintain con-
tact with the gaseous phase by penetration through the air bubble film while
the lamellar (or film) theory holds that the at t achment takes place without
penetration. Leja and Schulman (1954) state: "...as soon as the air bubble
contacts the solid surface [Figs. 3 and 4] the collector-frother molecules of
the air/water interface can now penetrate the diffuse monolayer at the solid,
and adsorb strongly on the solid surface, greatly increasing local surface con-
centration and local hydrophobic character of the surface."
The mechanism of particle-bubble adhesion suggested by Leja and Schul-
man could be considered an extension of the linear theory discussed by Wrobel
(1951-52). Several workers (Fuerstenau and Yamada, 1962; Lekki and Las-
kowski, 1971; Bansal and Biswas, 1974; Malysa et al., 1981a, b) with different
objectives on different mineral-collector-frother systems in their investiga-
tions confirmed frother-collector interactions and consequently the effects in
39
flotation, for example, in bubbl e-part i cl e collision, at t achment , stabilization,
etc. Despite t he i mport ance of such i nt eract i ons in flotation processes little
i nformat i on is available on t he choice or combi nat i on of a frot her for a given
collector (or mi neral -col l ect or) system. Cert ai nl y investigations of t hi s type
need quantitative dat a like frother and collector concentrations at t he air-liquid,
ai r-sol i d and solid-liquid interfaces, whi ch means very low concent rat i ons.
Al t hough Bansal and Biswas (1974) suggested t he use of C 14 radioactive la-
belled compounds for investigations of this nature, problems such as t hei r ready
availability, long half-life periods, high costs, envi r onment al restrictions, etc.,
make t he investigation impractical.
Among t he alcohols (et hyl to but yl ) studied as frot hers for t he flotation of
galena wi t h et hyl xant hat e as collector, Mukai et al. (1972) obt ai ned a bet t er
recovery wi t h amyl alcohol. The phenomenon was consi dered to be due to t he
mut ual co-adsorption of t he col l ect or-frot her molecules. It was explained on
t he basis of t he shift of t he wave number of t he C- H st ret chi ng vibration of
alcohols and xant hat es. The shift in t he asymmet ri c st ret chi ng vibration of
t he CH3 group around 2960 c m- 1 was found to be a funct i on of t he number of
carbon at oms in t he alkyl group (Figs. 5 and 6). Cert ai nl y dat a of t hi s type
would be useful in t he selection of a frot her for a given mi neral -col l ect or sys-
tem. However, furt her work along t hese lines on ot her systems is necessary for
a bet t er under st andi ng of t he i nt eract i ons and consequent l y t hei r effects on
t he yield paramet ers.
Classification of frothers
A frot her has a number of funct i ons in flotation - - first, it reduces t he sur-
face t ensi on of t he ai r-l i qui d i nt erface in order t hat a stable bubble is produced
in t he system; secondly, it influences t he kinetics of bubbl e-part i cl e adhesion;
thirdly, it t hi ns t he liquid layer by i nt eract i ng wi t h collector molecules and
finally, it stabilizes t he bubbl e-part i cl e aggregate ( Schul man and Leja, 1954;
Leja, 1956-57). Fl ot at i on froths are t hree-phase wi t h solids in t he froth. I n
addi t i on to t he frot her properties like surface activity, surface viscosity of t he
medium, etc., t he nat ure of solids, i.e. t he particle size and t he hydrophobicity,
play a domi nant role in i mpart i ng stability to t he froth. Lekki and Laskowski
(1975) classified t he frot hers i nt o surface-active and surface-inactive based on
t hei r mechani sm of action, i.e. t he ability to adsorb or co-adsorb on t he mi neral
surface wi t h a collector (Tabl e II and Fig. 7). They observed frot h stabilization
in t he presence of solids wi t h surface-inactive compounds such as di acet one
alcohol and et hyl acetal whi ch do not possess frot h-formi ng properties.
Effect of interaction products on froth
The stabilization or destabilization of froth is i nfl uenced by several factors
and no single t heory could explain t he mechani sm by whi ch t hese factors affect
40
3000
2990
E
u 2980
m
g
z 2970
<
2960
2950
/ I I I I
I I X A N T H A T (
o ALCOHOL
' ~ ~ o ~ . . . . o
I
I I I I I I
I 2 3 4 5 6
NUMBEROFCARBONATOMSINTHE ALKYL
CHAIN OFXANTHATE ORALCOHOL
Fig. 5. Relation b e t w e e n the w a v e n u m b e r of C H a stretching vibration a n d the n u m b e r of carbon
a t o m s in the alkyl chain of xanthate or alcohol ( M u k a i et al., 1972).
2 9 9 0
- - 2980
E
u
m 2970
<
2960
2950
I I [ I I
1 2 3 4 5
NUMBER OF CARBON ATOMS I N THE A L K Y L CHAI N
1 0 0
8 0
60
v ~
<
l.O o
d
u_
Fig. 6. C o m p a r i s o n of the floatability of galena w i t h the w a v e n u m b e r of alcohol ( M u k a i et al.,
1972).
t h e stability o f f r o t h . I n g e n e r a l , a r e d u c t i o n i n t h e v o l u m e o f f r o t h o r d e s t a -
bilization is k n o w n t o t a k e p l a c e d u e t o b u b b l e c o a l e s c e n c e , a n d t h e v a r i o u s
f a c t o r s w h i c h p r o m o t e o r l e a d t o c o a l e s c e n c e s h o u l d b e c o n s i d e r e d o n t h e b a s i s
o f e x p e r i m e n t a l c o n d i t i o n s . W a r k ( 1 9 3 8 ) o b s e r v e d a b s e n c e o f f r o t h w i t h sul-
p h i d e m i n e r a l s o n t h e a d d i t i o n o f x a n t h a t e w h i l e M o e l l e r ( 1 9 5 5 ) a n d L e j a a n d
S c h u l m a n ( 1 9 5 4 ) n o t i c e d a n i n c r e a s e i n f r o t h stability o n t h e a d d i t i o n o f x a n -
t h a t e i n t h e a b s e n c e o f m i n e r a l s . T h e n a t u r e o f s o l i d p a r t i c l e s - - t h e size, h y -
d r o p h o b i c i t y , c o n c e n t r a t i o n , s t a t e o f a g g r e g a t i o n , i n t e r a c t i o n p r o d u c t s f o r m e d
i n t h e p u l p - - e x e r c i s e i n f l u e n c e o n f l o t a t i o n f r o t h s . L i v s h i t s a n d D u d e n k o v
TABLE II
Classification of flotation frothers (Lekki and Laskowski, 1975)
4 1
G r o u p s C h a r a c t e r i s t i c o f I n t e r a c t i o n s a t t h e
a q u e o u s s o l u t i o n l i q u i d / g a s i n t e r f a c e
a t f l o t a t i o n r a n g e
o f c o n c n .
Froth
surface- colloidal solutions cause a large two- and three-
active (fatty acids, amines ) change in surface phase
tension
molecular solutions lower the surface two- and three-
(alcohols) tension of solutions phase
surface- molecular solutions do not alter the three-phase
inactive (diacetone alcohol surface tension froth only
and ethyl acetal)
inorganic raise the surface poor two-
electrolytes tension of solutions phase froth and
good three-
phase froth
with
hydrophobic
minerals
( 1965) t h o u g h t t h a t i t was i mpos s i bl e t o d e s t r o y t h e f r o t h e ve n a t a hi gh xa n-
t h a t e c o n s u mp t i o n i n t h e a bs e nc e of s ur f a c e oxi da t i on p r o d u c t s or h e a v y me t a l
i ons p r e s e n t i n t h e s us pe ns i on. A r e d u c t i o n i n t h e d y n a mi c a n d s t a t i c s t a bi l i t y
of f r o t h was obs e r ve d wh e n x a n t h a t e was a dde d t o f r o t h e r s ol ut i on c o n t a i n i n g
Q.
b.

sur f ace ac t i v e f r ot hef ) s u r f a c e i nac t i v e f r o t h e r
F i g . 7. M e c h a n i s m o f a c t i o n of: a. s u r f a c e - a c t i v e f r n t h e r ; b. s u r f a c e - i n a c t i v e f r o t h e r ( L e k k i a n d
L a s k o w s k i , 1 9 7 5 ) .
42
soluble salts of copper or lead (50 mg/1) ; wi t h zinc salts no such effect was
found. Si mi l arl y wi t h cal ci um or bar i um in t he frot her sol ut i on a sharp de-
crease in t he st abi l i t y of f r ot h was observed on t he addi t i on of sodi um oleate.
The presence of mer cur y xant hat e in t he pul p was f ound to weaken t he frot h
(Ray and Brewers, 1941). The soluble salts form hydrophobi c preci pi t at es
aft er i nt er act i on wi t h t he collector. The n t he effect of t hese preci pi t at es on
frot h shoul d be t he same as t hat of t he hydrophobi c solid particles. The size of
t he heavy met al preci pi t at e part i cl es f or med by react i on wi t h xant hat e was
f ound to be 0.2-0.5 t t m ( Gl embot sky and Kol chemanova, 1958). Li vshi t s and
Dudenkov (1965) i nt er pr et ed from t he work of Leja and Schul man (1954)
t hat t he preci pi t at e part i cl es adsorb t he f r ot her mol ecul es t hus l eadi ng t o a low
frot her concent r at i on in t he pul p and consequent l y causi ng a reduct i on in t he
st abi l i t y of frot h.
Effects of particles on f rot h
The i nfl uence of solids on f r ot h st abi l i zat i on is al ready well known. The
phe nome non was at t r i but ed to be due to an increase in vi scosi t y of surface
films. Kl assen and Mokr ousov (1963) observed t hat t he st r onger t he hydro-
phobi ci t y of t he part i cl e t he great er was t he effect in stabilizing t he frot h. The
fact t hat hydrophobi c solids can stabilize or destabilize t he f r ot h is dependent
on t he part i cl e size and t hei r concent r at i on. Li vshi t s and Dudenkov (1965)
believe t hat t he dest r uct i on of f r ot h by hydr ophobi c part i cl es is si ze-dependent
and f ur t her t hat t he coarser hydr ophobi c part i cl es mi ght even pr event bubbl e
coalescence by act i ng as buffers bet ween bubbles. The fine part i cl es t oo do not
affect t he coalescence rate. Ther e seems t o be an opt i mum size range for par-
ticles t o stabilize or destabilize t he frot h.
Lovell (1976) i nvest i gat ed t he f r ot hi ng charact eri st i cs of a phosphat e ore
cont ai ni ng essent i al l y apat i t e and calcite. Bot h mi neral s at low solid concen-
t r at i ons dest abi l i zed t he f r ot h in t he presence of t al l oil fat t y acid, and at hi gher
concent r at i ons t he f r ot h obt ai ned was more t han t he t wo-phase frot h, t hus
i ndi cat i ng frot h stabilization. Wi t h tall oil fat t y acid and ot her modi fyi ng agent s
apat i t e dest abi l i zed t he f r ot h i rrespect i ve of t he solid concent r at i on st udi ed
while calcite still had a stabilizing effect. Thi s behavi our was exami ned in t er ms
of hydr ophobi ci t y ( cont act angl es) and part i cl e size. The f r ot h dest abi l i zat i on
at lower solids concent r at i on was at t r i but ed t o hydr ophobi ci t y and i ncrease in
frot h st abi l i zat i on at hi gher concent r at i on of solids t o be due t o an i ncrease in
part i cl e size by aggl omerat i on. A si mi l ar expl anat i on t hat fl occul at i on of par-
ticles leads to i ncreased frot h st abi l i t y was pr esent ed by Dudenkov (1967).
Di ppenar (1982) measur ed t he effects of part i cl e size of hydrophobi c quart z
and galena on f r ot h vol ume. The effect of a mass of 0.16 mg of 4-6 ffm hydro-
phobi c quart z part i cl es on reduci ng t he i mmedi at e f r ot h vol ume was f ound to
be t he same as t ha t of 18.8 mg of 500- 589/ t i n size. Wi t h hydr ophobi c gal ena
t he masses requi red t o reduce t he f r ot h vol ume were 1.7 mg and 140 mg for
43
- - 1 2
s
- - t O
6
,V
4
2
Manual
o d i s p e r s i o n
Ul t rasoni c
x d i s p e r s i o n
x x
x x
10 100
Sol i ds concent r at i on mg t - l ( Li qui d)
1000
1 6
1 4
- - 1 2
~1o
2
i 8
~ 6
4
2
0
i
100
Solid concent rat i on gl-~(pulp)
1000
Fig. 8. Low futile concentration effect on froth stability (Hemmings, 1981 ).
Fig. 9. High rutile concentration effect on froth stability (Hemmings, 1981 ).
8 - 1 0 / ~ m and 9 0 - 1 0 6 # m si zes, respecti vel y. A si mi l ar i nves t i gat i on by He m-
mi ngs ( 1981) on - 8 / L m ruti l e parti cl es i n a s ol ut i on c ont ai ni ng 25 ppm ol eat e
wi t h 0. 2 ppm Fe +3 at a l ow sol i d c onc e nt r at i on s howe d a des t abi l i zi ng ef f ect
and at hi gher sol i d c onc e nt r at i on t he f rot h was f ound t o be st abl e ( Fi gs. 8 and
9 ) .
Re c e nt i nves t i gat i ons by Di ppenar ( 1982) on t he ef f ect s of part i cl es of di f-
f erent s hapes and degrees of hydrophobi ci t y on f i l m rupture wi t h an arti fi ci al l y
t hi nne d f i l m of wat er by hi gh speed ci nemat ography reveal ed s ome i nt eres t i ng
f eat ures ( Tabl e I I I ) . The equi l i bri um cont act angl e ( wi t ho ut rupt uri ng t he
f i l m) was es t abl i s hed i n t he case of spheri cal gl ass beads wi t h a cont act angl e
of 74 and t he f i l m was f ound t o rupture onl y on at t ai ni ng i ts nat ural rupture
t hi c kne s s . The parti cl e wi t h a cont act angl e of 102 rupt ured t he f i l m wi t hi n
mi l l i s econds of cont act wi t h t he l ower i nterface; rough parti cl es of quartz and
s ul phur wi t h a cont act angl e of > 90 were ori ent ed wi t h more t ha n hal f t he
body i n t he air phas e and wi t h < 90 t owards t he l i qui d phas e. Li vs hi t s and
Dude nko v (1960, 1965) and Dude nko v ( 1967) observed t hat very s mal l hy-
drophobi c part i cl es wi t h cont act angl es > 90 ruptured t he t hi n f i l ms be t we e n
bubbl es. Thi s occurred wh e n t wo bubbl es came i nt o cont act wi t h hydrophobi c
parti cl es, and each i nt erphas e whi l e t ryi ng t o es t abl i s h i ts equi l i bri um on t he
parti cl e t hi nne d t he f i l m i n be t we e n t he bubbl es f i nal l y res ul t i ng i n a rupture.
P A R T I C L E E N T R A I N M E N T
T h e t w o important m e c h a n i s m s b y w h i c h particle collection takes place in
a flotation operation are adhesion a n d entrainment. N o t m u c h information
exists o n the other possible m e c h a n i s m s like e n t r a p m e n t (Gaudin, 1957) a n d
carrier flotation (Greene a n d D u k e , 1962).
44
TABLE III
Effects of particles of different shapes and degrees of hydrophobicity on film rupture (data taken
from Dippenar, 1982)
Mineral Surface Si ze Treatment Contact Induction Total
nature (#m) angle time .2 interaction
(degr.) (ms) time *:~
(ms)
glass
beads Spherical
Spherical
Quartz Rough
Galena Sharp
rectangular/
smooth
Sulphur Smooth
Rough
250 DDMS *l 74 30 --
102 12 106
160 DDMS 7 10
160 98 5.5 9
160
K Hexyl 80 _+ 8 2 10
xanthate
70 8 --
In presence
of emulsified
paraffin 95 _+ 0.5 5 6
tDichlorodimethylsilane.
2The interval between apparent contact of the solid with the meniscus and formation of a three
phase boundary.
3The time taken to rupture the film (values shown in the table include the induction time).
Par t i cl e s i z e - - f l ot at i on a n d e n t r a i n me n t
The effects of particle and bubble sizes on fl ot at i on rate recovery were in-
vestigated by several workers; experi ment al studies and theoretical analysis
have led to varying results. These aspects were dealt wi t h in earlier works
(Trahar, 1976, 1981; Jameson et al., 1977; Szatkowski and Freyberger, 1985),
therefore only t he results reported by some workers are given in Table IV. The
influence of particle size on t he rate of recovery of minerals was investigated
by Gaudi n et al. (1931), Ant hony et al. (1975) and Tr ahar (1976). In indus-
trial concent rat ors t he recovery for copper, lead and zinc minerals was shown
to be maxi mum in t he size range of 10-100 ~tm (Gaudi n et al., 1931 ). While
t he slow recovery rate of fine particles was due to decreased particle-bubble
collisions, t hat of coarse particles was at t ri but ed to t he disruption of bub-
ble-particle aggregate in t urbul ent zones ( Morris, 1950; Schultze, 1977). One
of t he reasons for t he low fl ot at i on rate of coarse particles was t hat with in-
creasing particle size t he densi t y of t he bubble-particle aggregate approaches
t hat of t he pulp densi t y and t hereby t he aggregate becomes less buoyant
(Jameson et al., 1977 ). Tl ~ argument put fort h by Jowet t (1980) for the poor
recovery is in agreement with the observations made by Dippenar (1982). Wi t h
45
TABLE IV
Relationship between the flotation rate constant k and the relative diameters of particles (dp)
and of air bubbles (rib) where indicated
(a)
(b)
(c)
(d)
(e)
(f)
(g)
k independent of particle size for dp = 1-4
#m (galena)
h~:dp for dp=4-28#m (galena)
h ~: dp/ db 2
kocln dp
k independent of dp
koc dp 2 (for apatite, hematite and galena)
kocd, ; d,=4-20/lm (quartz)
(h) k ~c dp2 / db 3
(i) k~c 1/db ~
Gaudin et al. (1942)
Gaudin et al. (1942)
Sutherland (1948)
Morris (1952)
Bushell (1962)
Tomlinson and Fleming
(1963)
Tomlinson and Fleming
(1963)
Reay and Ratcliff {1973)
Jameson et al. (1977)
i ncr easi ng par t i cl e size t he i nduct i on t i me i ncr eases a nd hence poor fl oat abi l -
ity. I n addi t i on t o t he par t i cl e size a nd sur f ace chemi cal char act er i st i cs, t he
shape f act or also seems t o i nf l uence t he i nduct i on t i me (see Tabl e I I I ) .
For bubbl e- par t i cl e adhesi on it is necessar y t ha t t he bubbl e shoul d collide
wi t h t he par t i cl e and cons equent l y fi l m r upt ur e will follow by t he est abl i sh-
me nt of a t hr ee- phas e cont act . Wher eas t he e nt r a i nme nt is a char act er i st i c
f eat ur e of fi ne par t i cl es and is non- sel ect i ve, t her e bei ng no di st i nct i on be-
t ween hydr ophi l i c or hydr ophobi c part i cl es. An ar bi t r ar y cl assi fi cat i on of par -
t i cl es i nt o fi ne ( 5- 10 ~m) , i nt er medi at e ( 10- 70/ l m) a nd coarse ( > 70 #m) on
t he basi s of t hei r fl oat abi l i t i es was di scussed by Tr a ha r (1981). It is, of course,
di ffi cul t t o general i ze si nce t he fl oat abi l i t i es var y f r om mi ner al t o mi ner al , as
can be obser ved f r om Tabl e V. However , i t is known t ha t t he adhesi on of par -
t i cl es > 10 #m i n size occurs due t o collision wi t h ai r bubbles. For par t i cl es < 10
#m t he collision effi ci enci es ar e low and t he me c ha ni s m of col l ect i on t akes
pl ace by e nt r a i nme nt , i.e. t he par t i cl es ar e car r i ed i n t he liquid sept a f or mi ng
t he bubbles.
I n gener al t he hi gh recoveri es obt ai ned i n f l ot at i on ei t her at pl ant level or i n
bat ch t est s ar e not separ at el y account ed for i n t er ms of r ecover y by ent r ai n-
me nt a nd by t r ue fl ot at i on. The cont r i but i on t o t he fi nal yi el d by e nt r a i nme nt
is si gni fi cant especi al l y wi t h fi ne par t i cl es pr es ent i n t he syst em and i t is i m-
por t a nt t o es t i mat e t hi s f act or for a bet t er eval uat i on of t he process
per f or mance.
D e g r e e o f e n t r a i n m e n t
The e nt r a i nme nt of par t i cl es i n f l ot at i on is cl osel y r el at ed t o t he r ecover y of
wat er. Several wor ker s i nvest i gat ed t he effect s of oper at i ng vari abl es like f r ot h
46
TABLE V
Observed size ranges of fl ot at i on recovery for different minerals as report ed by different workers
(from Tr ahar and Warren, 1976)
Mineral Size range Condi t i ons Reference
(~m)
Baryt es 10- 30 laboratory, Clement and Klossel (1963)
bat ch
Cassiterite 3- 20 i ndust ri al Kelsall et al. (1974)
Fl uori t e 40-110 l aborat ory, Klassen and Mokrousov
bat ch {1963, p. 390)
10- 90 i ndust ri al Klassen and Mokrousov
(1963, p. 390)
50-150 i ndust ri al Lay and Bell {1962)
Galena 37-295 l aborat ory,
bat ch Gaudi n et al. (1931)
170-240 laboratory, Klassen and Mokrousov
bat ch (1963, p. 391)
7- 70 i ndust ri al Cameron et al. (1971)
6- 70 i ndust ri al Kelsall et al. (1974)
13- 75 i ndust ri al Klassen and Mokrousov
(1963, p. 391 )
20-100 i ndust ri al Lynch and Thor ne (1974)
Pyri t e 50-100 l aborat ory, Imai zumi and Inoue {1965)
cont i nuous
Pyri t e- 20- - 70 laboratory,
pyr r hot i t e bat ch Morris (1952)
Quartz 10- 40 laboratory, De Bruyn and Modi (1956)
cont i nuous
9- 50 laboratory, Robi nson (1959)
bat ch
Sphal eri t e 15-100 i ndust ri al Cameron et al. (1971)
8- 70 laboratory,
bat ch Ant hony et al. (1975)
Wolframite 20- 50 laboratory,
bat ch Cl ement et al. (1966)
de pt h, f rot her c o n c e n t r a t i o n a nd air a ddi t i o n whi c h i nf l ue nc e t he wat e r recov-
ery. Mi t r o f a n o v et al. ( 1985) p o i n t e d o u t t h a t t he f act ors r e s pons i bl e f or e n-
t r a i n me n t are t he a s c e ndi ng a nd de s c e ndi ng s t r e a ms as a r e s ul t o f cel l
hy dr o dy na mi c s , bubbl e p o p u l a t i o n a nd si ze, a mo u n t o f s l i me s a nd t h e c o nc e n-
t r a t i o ns o f t he reagent s .
Wr obe l ( 1 9 5 3 ) , i n an i nv e s t i g a t i o n o n f l o t a t i o n f rot hers , o bs e r v e d a di rect
r e l at i ons hi p b e t we e n wat e r c o n t e n t i n t he f rot h a nd t he c o nc e nt r a t e grade. Th e
TABLE VI
Degree of entrai nment for different minerals
Mineral Sp.gr. Particle size Degree of Reference
(/~m) entrai nment
Quartz 2.65 3.5 0.72
> 40.0 0.10
Silica < 12.0 0.99
Cassiterite 6.80-
7.10 < 5.0 0.85
Coal 1.00-
1.80 < 38.0 1.00
Ultraf'me gangue 0.87 Warren (1985)
Fine gangue < 40.0 0.78 Subrahmanyam and
Forssberg (1986)
47
Trahar (1981)
Engelbrecht and
Woodburn (1975)
Engelbrecht and
Woodburn (1975)
Goodman and Trahar
(1977)
Lynch et al. (1981)
varyi ng behavi our of a mi neral ( f l ot at i on and e nt r ai nme nt ) wi t h di f f erent si ze
fracti ons present i n t he pul p is evi dent f rom t he work of Engel brecht and
Woodburn (1975) and Subrahmanyam and Forssberg (1986). Engel brecht and
Woodburn (1975) observed a l i near rel at i onshi p wi t h water recovery i n t he
case of hydrophobi c pyri te < 7.7/~m and si l i ca < 12/~m. The recovery of coarse
pyri te 20- 27/ i ra was f ound to be dependent on hydrophobi ci ty. A si mi l ar ob-
servati on was made by Subrahmanyam and Forssberg (1986) i n an i nvest i -
gati on on t he performance of di f f erent f l ot at i on frothers wi t h a copper ore
~containing graphite and si l i ca i n major proportion. For hydrophobi c parti cl es
t he recovery by ent rai nment was measured by di fferences i n t he relative con-
t ri but i ons of true f l ot at i on i n t he presence of col l ector and by ent rai nment i n
t he absence of t he collector, i.e. wi t h frother onl y present at t he same water
recoveries (Trahar, 1981 ). The rel at i onshi p bet ween t he recovery of f i ne gan-
g ue by ent rai nment and t he recovery of water i s represented by t he equation:
Rg----eg Rwater (1)
where Rg is t he recovery of f i ne gangue of a gi ven si ze i n a gi ven t i me, eg a
cons t ant for a gi ven parti cl e si ze and speci fi c gravity and Rwat~r is t he recovery
of water for t he same t i me. The slope of t he l i ne eg i n t he pl ot of t he recovery
of solids versus t he recovery of water is t ermed t he degree of ent rai nment and
t he val ues reported by several workers are gi ven i n Tabl e VI.
For hydrophobi c parti cl es, Warren (1985) proposed:
Rm=Fm+em Wwat~r ( 2)
45
TABLE VII
Liquid lameUa thickness (data taken from Hemmings, 1981 )
Circuit Lamella
thickness in
different cells
(/zm)
Coal 280- 830
Copper 70- 340
Lead 70- 290
Zinc 80- 210
Tin 50- 130
Scheelite 60-1080
where Fm is t he i nt ercept of t he ext rapol at ed line on t he mi neral recovery axis
i ndependent of wat er recovery and em is t he ent r ai nment factor for floatable
( hydrophobic ) mineral.
Liquid lamella thickness-entrainment
Hemmi ngs (1980) concluded t hat t he thickness of t he aqueous lametla would
be t he principal factor for t he concent rat i on of ul t rafi nes ( - 10/ an) . In a l at er
investigation Hemmi ngs (1981) measured t he frot h liquid lamella t hi ckness
with a specially developed conduct i vi t y probe in di fferent beneficiation pl ant s
( Table VI I ) . He found t hat t he frot h liquid lamella t hi ckness was far too high
for t he concent rat i on of ul t rafi ne particles whi ch would otherwise be possible
if t he liquid lamella were t hi nner t han 10-20 pro. Thi s observation holds for
t he liquid t hat is carried by t he bubbles (or t he liquid septa forming t he bub-
bles). The t hi cker t he liquid lamella t he higher is t he wat er cont ent and hence
greater is t he possibility of fine particles being recovered by ent r ai nment rat her
t han by t rue flotation.
DRAINAGE
The particles are carried into t he froth by rising bubbles t hrough t he pulp
phase. These bubbles wi t h t hei r load of particles accumul at e at t he pul p/ frot h
interface. A variable amount of t he mat eri al carri ed i nt o t he frot h ret urns to
t he pulp by drainage. The re-ent ry of particles into t he pulp occurs because of
t he cont i nuous drai nage of liquid and bubble coalescence. Al t hough several
factors described above cont ri but e to bubble coalescence whi ch can lead to
drainage of hydrophobic particles also, but little evidence on t hi s aspect elim-
inates this possibility. The drai nage of gangue particles is desirable from t he
view poi nt of enri chi ng t he grade. It was suggested t hat wat er sprayi ng on t he
49
froth layer mi ght improve bot h grade and recovery (Kl assen and Mokrousov,
1963). Obviously t hi s accelerates t he liquid drai nage and hence t he drainage
of gangue material.
Recent investigations of Cut t i ng and Deveni sh (1975), Moys (1978, 1984),
Cut t i ng et al. (1981, 1982, 1986), Kuzki n et al. (1983) and Mi t rofanov et al.
(1985) have given an insight into t he possible mechani sms operat i ng in t he
flotation froths.
Investigations carried out by Moys (1978) deal wi t h t he mi neral concent ra-
t i on gradients, frot h properties and t he effect of froth removal on frot h grades
wi t h respect to froth height. A steady increase in t he grades of Cu, Zn and Fe
sulphides and percent age of solids in t he froth and a decrease in t he gangue
grade wi t h increasing froth height were observed. Above a cert ai n froth height
t he concent rat i on of t he gangue was found to be const ant .
The di spl acement of less hydrophobic (Fe) by more hydrophobic (Cu, Zn)
particles in t he froth was at t ri but ed to t he lower film surface area as a result
of drainage and bubble coalescence. Cut t i ng et al. (1981) explained t hi s in
t erms of t he degree of hydrophobi ci t y of t he mi neral particles and t he degree
of competition; while t he former is an effect of t he chemi cal envi r onment t he
l at t er is a consequence of t he machi ne operat i ng variable. And finally t he frot h
st ruct ures det ermi ne t he appearance of t he mi neral species dependi ng on t he
degrees of hydrophobicity.
A general conclusion from t he investigations of Cut t i ng et al. (1986), Moys
(1984) and Kuzki n et al. (1983) is t hat t he convent i onal flotation cells in
whi ch t he froth is removed by mechani cal means will cause froth collapse re-
sulting in recovery losses. I n order to allow maxi mum drainage, t he removal of
t he upper frot h layers only is recommended. Bisshop and Whi t e (1976) have
shown t hat t he residence t i me is t he most i mpor t ant factor in t he particle
recovery.
SUMMARY AND CONCLUSIONS
The frot h forms an i mpor t ant phase in flotation but t here has been relatively
little work on t he several factors t hat govern its stability and t he mechani sms
wi t hi n t he froths. Fr ot h behavi our is different under different experi ment al
condi t i ons and is i nfl uenced by t he system variables - - physical, chemical and
geometrical and t hei r interactions. As many of us have observed, even in t he
same flotation circuit mi neral i zed froths behave differently, i.e. vari at i on of
bubble sizes and stability in rougher, scavenger and cl eaner cells. Thi s could
be explained to a cert ai n ext ent by online measurement s such as reagent con-
cent rat i ons, i nt eract i on product s formed, particle sizes and concent rat i ons, air
flow, etc.
Although t here is general agreement on t he format i on of i nt eract i on prod-
ucts in flotation, t hei r influence on frot h is controversial. The frot her-col l ect or
50
c ombi na t i ons , t h e i r i n t e r a c t i o n s wi t h mi ne r a l s a n d c o n s e q u e n t l y t h e i r ef f ect s
on pr oc e s s ne e d f u r t h e r i nve s t i ga t i ons .
Th e e n t r a i n me n t is una voi da bl e wi t h f i ne pa r t i c l e s p r e s e n t i n t h e s ys t e m
a n d t he r e c ove r y of hydr ophi l i c gangue is cl os el y r e l a t e d t o t he r e c ove r y of
wat er . By ma n i p u l a t i n g t h e va r i a bl e s t h a t a f f e c t t h e r e c ove r y of wat er , b e t t e r
gr ades a n d r e c ove r i e s c a n be obt a i ne d. Bo t h t h e r e s i de nc e t i me of t h e f r o t h a n d
f r ot h r e mova l me c h a n i s ms i n f l ot a t i on cel l s i nf l uence t he r ecover i es a n d gr ades.
For e xa mpl e , i n t he a bs e nc e of f r ot h r e mova l hi ghe r gr ades of f l oa t a bl e mi n-
er al s a n d l ower gangue mi n e r a l c o n c e n t r a t i o n s we r e obs er ved. Wi t h l onger
f r o t h r e s i de nc e t i me s t he e n t r a i n e d hydr ophi l i c pa r t i c l e s dr a i n ba c k t o t he pul p
t h u s yi el di ng a hi gh gr ade c o n c e n t r a t e , whe r e a s hi gh r e c ove r i e s a n d l ow gr ades
woul d r e s ul t f r o m s h o r t e r r e s i de nc e t i mes .
Re c e nt i nves t i gat i ons on dr a i na ge me c h a n i s ms ha ve pr ovi de d a n i ns i ght i nt o
t he o p e r a t i n g me c h a n i s ms of t h e f r o t h pha s e . I t ha s b e e n s h o wn t h a t si ze cl as-
s i f i cat i on occur s on t he bas i s of h y d r o p h o b i c p r o p e r t i e s ( de gr e e of h y d r o p h o -
b i c i t y ) . De p e n d i n g on t hi s t h e pa r t i c l e s a p p e a r i n t h e f r o t h l a ye r whi c h i n t u r n
is di c t a t e d by t he f r o t h mobi l i t y s t r uc t ur e s . Mo r e knowl e dge is ne c e s s a r y on
t he dr a i na ge as pect s .
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