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Minerals Engineering 20 (2007) 1303–1308

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Frother analysis: Some plant experiences

Stéphanie Gélinas a, James A. Finch b,*

a
Échem Technologies Inc., 558 De La Métairie, Verdun, Québec, Canada H3E 1S5
b
Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montréal, Québec, Canada H3A 2B2

Received 16 March 2007; accepted 26 July 2007

Available online 11 September 2007

Abstract

A colorimetric technique, originally developed for methyl iso butyl carbinol (MIBC) based on the Komarowsky reaction, has been
extended to a wide range of common mineral flotation frothers. The procedure, which is briefly described, is suited to on-site determi-
nation as shown in a series of industrial case studies. Some observations described include: distribution of frother down a bank and
between pulp and froth; evidence of alcohol contaminants; and mass balancing. The ability to monitor frother will help interpret cell
hydrodynamics and should help optimize the type, amount and location of frother addition.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Froth flotation; Flotation frothers; Mass balancing

1. Introduction processing sulphide ores. The availability of portable visi-

Owing to lack of analytical methods, the task of deter-
mining frother concentration in flotation circuits is not
routinely performed. Industrial sites seldom outsource
analyses that are costly and inconvenient. A colorimetric
method has recently been demonstrated for on-site charac-
terization of common industrial frothers (Gélinas and
Finch, 2005; Gélinas et al., 2005). The approach, based
on the Komarowsky reaction (Penniman et al., 1937; Coles
and Tournay, 1942; Duke, 1947), was previously described
by Parkhomovski et al. (1976) for methyl iso butyl carbinol
(MIBC). The reaction involves the interaction of the OH
group of a higher alcohol, concentrated sulphuric acid,
and salicylaldehyde to yield coloured solutions that can
be analyzed by UV–visible spectrophotometry.
Gélinas and Finch (2005) reviewed the general colori-
metric reactivity with salicylaldehyde of a range of frothers,
including typical aliphatic alcohols, cyclic alcohols, phe-
nols, and alkoxyparaffins. The method proved largely
insensitive to other reagent additions typically encountered
*
Corresponding author. Fax: +1 514 398 4492.
E-mail address: jim.finch@mcgill.ca (J.A. Finch).
ble spectrophotometers and the adaptability of the sensi-
tive procedure, make on-site determination feasible.
The ability to measure frother should help plants iden-
tify the amount and location of frother addition to opti-
mize the process and to assess frother in reclaim water or
in effluent streams. The information could be extended to
help identify the type of frother to be used and to integrate
frother use in control of cell hydrodynamics (the initial
impetus for the work).
To evaluate the colorimetric technique, the method was
first tested on-site as part of a cell hydrodynamics evalua-
tion campaign at Rio Tinto’s Copperton concentrator
(Utah, USA) (Gélinas et al., 2005). The procedure has sub-
sequently been exploited at other sites, which forms the
basis for this communication.
2. Experimental
2.1. Materials
All chemicals in the analytical procedure were used
as received from Sigma–Aldrich (USA). Note that only
chloroform stabilized with ethanol can be used to avoid

0892-6875/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2007.07.008
1304 S. Gélinas, J.A. Finch / Minerals Engineering 20 (2007) 1303–1308
cross-reaction of the stabilizer. The alcohols methyl iso
butyl carbinol (MIBC) and 3-methyl-1-butanol were also
from Sigma–Aldrich (USA). (The butanol was included
not as a frother per se but as it is a contaminant alcohol in
the xanthate supply at one plant.) The polyglycol frothers
F-150 and Unifroth 250C (U250C) were supplied by Flottec
(USA) and Huntsman & Reliable (Canada), respectively.
2.2. Sample preparation for colorimetric analysis
Standards are made-up of 0.05–0.2 mg of frother in
100 mL of tap water at room temperature. Solutions from
decanted supernatant pulp (or froth) samples are likewise
prepared, using appropriate dilution factors (based on esti-
mated concentration from dosage rate and pulp density).
The samples are neutralized by dropwise addition of dilute
sulphuric acid (1:10), and the pH is adjusted to 6.5–7. To
reduce foaming, 20 g sodium chloride per 100 mL sample
is introduced. The samples are added to a 250 mL separa-
tory funnel and two successive 10 mL extractions in chloro-
form are performed. The mixed phases are vigorously
shaken for two minutes, the aqueous phase is removed
and the bottom layer is transferred to another 50 mL separ-
atory funnel. Extraction to the reaction medium is achieved
by adding 10 mL of 3:1 sulphuric acid in water, shaking for
two minutes, and finally transferring the bottom layer to a
25 mL sealed glass vial.
2.3. Reaction
The reaction is initiated by the addition of 0.1 mL of 5%
salicylaldehyde in a 1:1 solution of acetic acid in water.
After mixing, the samples are placed simultaneously in a
bath of vigorously boiling water. The reaction is stopped
after exactly 20 min, by immediately immersing the sam-
ples in ice water, from which each vial is removed only
when its turn comes for colorimetric analysis. Since the
reaction is not allowed to go to completion, but is rather
arbitrarily stopped, it is necessary to run standards and
sample side by side under identical conditions.
2.4. UV–visible analysis
After the sample has reached room temperature, it is
transferred to a 1 cm2 visible cell for colorimetric analysis.
The absorption spectra are scanned with a UV–visible
spectrophotometer (Thermoelectron Genesys 10 Scan-
ning). The reference sample is tap water subjected to the
same reaction procedure. For reference, the two alcohols
have a maximum absorption between 520 and 560 nm
and the polyglycols a lower range, 490 nm (U250C) to
500 nm (F-150).
2.5. Sampling
Specific pulp volumes were extracted from selected flota-
tion cells using a manual perch sampler, at a depth well
below the froth surface. Froth samples were taken from
concentrate overflows using a pan.
3. Results and discussion
3.1. Frother profile in froth and pulp
This was the first survey, conducted at Rio Tinto’s
Copperton concentrator. The plant uses MIBC, an ali-
phatic alcohol, as frother and the profile (concentration
down a bank) and distribution between the pulp and froth
phases in a rougher/scavenger row (recovering bulk cop-
per/moly) is shown in Fig. 1. The profiles were constructed
by analysis of samples from selected cells in the row. The
results correspond to the calculated solution strength of
around 10 ppm, obtained from an average initial MIBC
addition of 0.02 kg/mt (0.04 lb/st) of dry feed in cell 1
assuming 33 wt.% solids, and a minor subsequent addition
of 0.003 kg/mt (0.006 lb/st) in cell 6.
The concentration in the pulp phase remains steady
throughout the row. The profile in the froth indicates an
increasing concentration down the bank. Some transfer
of frother to the froth (via adsorption on the bubble) is
anticipated, but the increase down the bank suggests
unknown system interactions at play modulated by the
presence of solids and variations in gas rate. While a con-
comitant decrease in pulp phase concentration should
result the relatively small flow of froth product in this
rougher stage compared to the pulp flow obscures any
changes. Analysis of the process water showed the presence
of 0.3 ppm MIBC, indicating the sensitivity of the
technique.
3.2. Frother profile following sequential addition
This campaign was conducted at Xstrata Zinc’s Bruns-
wick Mine operation (New Brunswick, Canada). The lay-
out of the rougher row is presented in Fig. 2. It
comprises four banks of four cells each, with MIBC (and
xanthate) addition at the head of each bank. The corre-
sponding frother distribution is roughly 55%, 20%, 15%
and 10%. Samples were taken at the top of the pulp phase
25
MIBC Concentration, ppm
20
15 Froth
10
5
Pulp
0
1 2 3 4 5 6 7 8 9 110 111
Cell number in Rougher/Scavenger Row
Fig. 1. Pulp and froth phase frother profiles in a selected rougher/
scavenger row (Rio Tinto’s Copperton concentrator).
 S. Gélinas, J.A. Finch / Minerals Engineering 20 (2007) 1303–1308 1305

Fig. 2. Row schematic showing frother addition points and (above) frother concentration for selected cells (Zinc Rougher row at Xstrata Zinc’s
Brunswick Mine).

(T) and at the bottom (B), close to the impeller, to check
distribution within the cell, along with samples of two
water sources, process water (PW) and quarry water (QW).
The results corresponding to the cell locations indicate
comparable concentrations at the top and bottom, suggest-
ing frother is well mixed throughout a cell. The initial con-
centration is ca. 3.5 ppm that steps up with each addition
to reach ca. 5 ppm. The additions, therefore, do not pri-
marily replace frother (e.g., lost to froth) but progressively
increase the pulp concentration. Process and quarry water
carry approximately 1 ppm of MIBC.
3.3. Frother distribution around a rougher/scavenger/cleaner
circuit
As part of a developing program to integrate frother use
in control of cell hydrodynamics, a survey was conducted
at Inmet’s Troilus Cu/Au concentrator (Québec, Canada).
Fig. 3a shows the pulp phase profile of F-150 (a polyglycol)
in the rougher-scavenger row. A small variation around ca.
0.55 ppm is observed down the bank of seven cells. Traces
of F-150 (0.09 ppm) were detected in the process water.
The results for cleaner cells 3, 7, and 12 show a sharp
difference (Fig. 3b). Substantial amounts of frother were
detected in these pulp samples. The origin of the large dif-
ference between roughers and cleaners is not fully under-
stood. Factors being evaluated range from interference
with the analysis (see later) to high recovery of F-150 to
the rougher froth (concentrate) to the impact of recycle
flows internal and external to the cleaner bank. The high
values in the cleaner cells did correlate with the ‘creamy’
appearance of the froth, and with hydrodynamic surveys
that showed only low gas rates could be tolerated in the
cleaner cells without flooding.

1.0 100
F-150 Concentration, ppm
F-150 Concentration, ppm

0.8
75
0.6
50
0.4

0.2 25

0 0
Feed 1 2 3 4 5 6 7 Tails cleaner 3 cleaner 7 cleaner 12
Sample ID Sample ID

Fig. 3a. Frother distribution in pulp samples of a rougher-scavenger row Fig. 3b. Frother concentration in selected cleaner cells (Inmet’s Troilus
(Inmet’s Troilus Concentrator). Concentrator).
1306 S. Gélinas, J.A. Finch / Minerals Engineering 20 (2007) 1303–1308
3.4. Frother distribution around a copper/zinc circuit
As part of the same program at Troilus a survey was
conducted at Agnico-Eagle’s Laronde operation (Québec,
Canada). The results for the distribution of MIBC at
selected points around the Cu-circuit are presented on the
flowsheet in Fig. 4. The results indicate an apparently sig-
nificant amount of MIBC (45 ppm) is already present after
the single frother addition to the primary conditioning
tank. The concentration remains near this level through
the roughing and scavenging sections. The cleaning circuit
shows about half this concentration level, suggesting dilu-
tion possibly by launder water. The most dilute is the final
cleaner, supporting that there is progressive dilution. The
results (not shown) for the Zn-circuit match those for the
Cu-circuit: about 40 ppm in roughing/scavenging decreas-
ing progressively through cleaning to ca. 10 ppm.
The results do not correspond to the known amount of
MIBC added which should give ca. 6 ppm in the primary
conditioner. A concentration of 3.6 ppm was measured in
the recycle water thus there is no build-up from that source.
The current suspicion is that there is a contribution of alco-
holic components originating from other reagents added to
the circuit. Xanthates, for example, often carry residual
alcohol from formulation, which is considered inert and
therefore not necessary to remove (Cappuccitti, 2005).
Since the colorimetric technique cannot distinguish
between different aliphatic alcohols (similar maximum
MIBC: 0 – 6 g/t
Primary Conditioning
45.1ppm
Scavenging:
Contact & Mechanical Cells
42.4ppm
TO ZINC CIRCUIT
Fig. 4. Apparent frother distribution in the copper circuit (Agnico-Eagle’s Laronde concentrator).
peak absorption), the results reported probably reflect the
total contribution of alcohol present in the pulp water. A
systematic evaluation of the alcoholic components in the
range of reagents added at the plant is required.
The next case study where a polygylcol frother was
employed gave a chance to test this interference from con-
taminant alcohol.
3.5. Mass balance exercise
CVRD INCO’s Clarabelle concentrator (Ontario, Can-
ada) uses Unifroth 250C frother (a polyglycol) and reports
up to ca. 5% alcohol (3-methyl-1-butanol) in their xanthate
supply. The objectives were first to demonstrate the two
reagents could be de-coupled for independent analysis
and, second, to collaborate with a mass balance exercise
to try to account for both reagents around the circuit. Since
polyglycol and the alcohol have different maximum peak
absorption, this allowed conventional simultaneous
analysis.
Fig. 5 presents the flowsheet indicating the reagent addi-
tion locations (arrows) and our sampling points (dots). The
concentrations are expressed in ppm of U250C (left hand
number) and 3-methyl-1-butanol (right). The pertinent
observations are: the concentration of frother and alcohol
is similar in magnitude; after each addition frother concen-
tration increases; frother (and to some degree the alcohol)
Roughing:
Primary Cleaning:
Column cells
Column & Contact cells
COPPER
CONCENTRATE
48.3ppm
19.3ppm
43.4ppm
28.3ppm
Secondary Cleaning:
Contact, Column,
Mechanical & Tank Cells
44.9ppm
24.0ppm
12.6ppm
 S. Gélinas, J.A. Finch / Minerals Engineering 20 (2007) 1303–1308 1307

Feed
U250C – Methyl Butanol
0 – 1.0
Mag Cleaners 0–0 Roughers/Scavengers
MAG- CLNR
1.7 -4.0
1.7-4.0 6.4 – 4.5 7.7 – 4.1 10.9 – 6.6
4.8 – 6.6 AA BB C D
SCAVENGER

MAG- RCLNR
27.9 – 10.2
4.5 – 6.9 14 5.6
14 – 5.6
11.9 – 10.4
Cleaner
“B” Cleaner

22 – 7.3
23.8 – 15.7
SCAV-- CLNR

Scavenger Cleaners
4.8 – 6.6 SCAV-- RCLNR

10.2 – 5.3
22 – 7.3

CONCENTRATE B CONCENTRATE A ROCK TAILS

Fig. 5. Flowsheet with frother addition points and sampling locations with corresponding U250C and 3-methyl-1-butanol concentrations (CVRD INCO’s
Clarabelle mill).

concentrates through the cleaning circuit; and significant
frother remains in the tails.
The de-coupling of the frother and contaminant alcohol
is a positive for the technique but the practical concern
whether the alcohol has any effect on the process remains.
The finding led to including 5-carbon alcohols in frother
characterization work which suggested an effect on bubble
size cannot be ruled out at the concentrations detected here
(Azgomi et al., 2006). The progressive increase in concen-
tration as frother is added, as in the Brunswick case, does
suggest there is little foundation for concern sometimes
expressed that frother is depleted through a circuit. Indeed,
it has led to a significant concentration of frother in the
cleaners, which may not be desirable.
At the same time as the frother analysis work was being
conducted plant personnel carried out a mass balancing
exercise. Water flow rates were made available which per-
mitted a first attempt at mass balancing the frother (and
alcohol). Fig. 6 shows mass flows ‘‘in’’ and ‘‘out’’ of the cir-
cuit for U250C. A total of 15.11 kg/h was added ‘‘in’’ the
circuit (13.07 kg/h to the non-mag circuit and 2.04 kg/h
16
Calculated amount of U250, kg/h
to the mag circuit) and the total frother ‘‘out’’ was esti-
mated at 15.99 kg/h, (9.66 kg/h in the rock tails, 3.5 kg/h
in concentrate B, and 2.83 kg/h in concentrate A); i.e.,
the balance closed to within 6%. A similar exercise for
the 3-methyl-1-butanol showed an estimated total of
11.02 kg/h ‘‘in’’ and total ‘‘out’’ of 11.94 kg/h, a discrep-
ancy of 8%.
4. Conclusions
The colorimetric technique for frother analysis was dem-
onstrated in a series of on-site investigations, including
simultaneous analysis in the case of an alcohol and a poly-
glycol. Findings of potential practical importance are: for
MIBC and U250C (but perhaps not F-150) there is little
evidence of frother depletion in the pulp liquor through a
circuit which is an argument against sequential addition
(that may cause problems of excess frother build-up); a cor-
ollary is that most frother remains in the pulp, exiting with
tails; and, contaminant alcohols can be present from other
reagent additions (the case of alcohol in xanthate is
detailed) that may interfere with the analysis (and may
have effects on the process). Together with the demon-
strated ability to mass balance, the way is opening for more

Mag control over frother selection and addition.

14

12 Acknowledgement
10 Non

8
Mag
The funding for this work was initiated under a Collab-
orative Research and Development grant from the Natural
6
Sciences and Engineering Research Council of Canada
4 (NSERC) with industrial sponsorship from (giving the ori-
2 ginal names, 2001) Inco, Teck-Cominco, Falconbridge,
0
Noranda, COREM, and SGS Lakefield Research. The
"in" "out " "out" "out" authors wish to thank the many personnel who enthusias-
rock tails conc B conc A tically collaborated in the site work and the companies
Fig. 6. Overall balance obtained for U250C frother (CVRD INCO’s mentioned for supporting the project and giving permis-
Clarabelle mill). sion to present the findings.
1308 S. Gélinas, J.A. Finch / Minerals Engineering 20 (2007) 1303–1308
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