Cationic flotation of iron ores: amine

characterization and performance

R.M. Papini, P.R.G. Brandlo and A.E.C. Peres
Graduate Student and Professors, respectively, UFMG - Federal
University of Minas Gerais, Belo Horizonte, Minas Gerais, Brazil

Abstract
In this int,estigation, the differences in the absorption spectra of etheramines, fatty atnines and condensates,
mostly present as acetates, from several suppliers are characterized by means of infrared spectrometry.
Sharp differences were observed in the absorption spectra of three Qpes of atnines and derit,atives.
Etheramines sho~va characteristic and well-defined peak at 1,114 em-'. This peak is due to the ether C - 0
group and differentiates etherarnines from the other classes. The abserzce of such a peak indicates that the
species is not an etheramine. The distinction between coizdensates and fatty amines is made by the presence
of a sharp peak around 3,200 cm-I. This peak is probably due to the proximity of the N-H atnirle groups and
C=O carbon$ groups in the atnide portion ofthe condensate's molecule and by difjerent and better-dejned
bands in the 1,800- to 1,500-em-]range. The,flotation perjormance of these amines was eval~tatedby means
of the laboratory-scaleflotation of an itabirite ore. The etheramines proved to be the most effective collectors
for this systetn. Monoamirles presented better performance than diamines for the ore under investigation.
Key words: Cationic collectors, Iron ore flotation, Infrared spectroscopy

Introduction Amines must be transformed into salts to improve their

Cationic collectors were utilized industrially in flotation for
the first time in 1935, much later than xanthates and fatty
acids. Cationic collectors are usually used to float minerals
that present anegative surface charge (Dudenhov et al., 1980).
Arnines are compounds of great importance in the field of
mineral technology. Their major use is in the cationic reverse
flotation of low-grade iron ores. However, they are also
employed in the flotation of silvinite ores, oxidized zinc ores,
phosphate ores (to remove quartz and silicate gangue) and
other industrial minerals systems. The collectors most fre-
quently used in the cationic reverse flotation of low-grade iron
ores belong to the group of the monoetheramines. Diamines
are also utilized in a Brazilian concentrator whenever low-
silica concentrates are required. Fatty alkyl amines are the
usual collector in silvinite flotation. Due to their low cost,
condensates are employed in the cationic flotation of silicate
impurities from phosphate ores. Combinations of amines
among themselves and with neutral molecules (such as fuel
oil) deserve increasing attention among mineral-processing
researchers.
The aliphatic amines are considered as derivatives from
paraffin hydrocarbons or as alkyl derivatives from ammonia.
Depending on the number of alkyl radicals, the amines are
classified as primary, secondary or tertiary. All the amines
bind with water to form products of substitution of the ammo-
nium hydroxide. The reactions are based on the alkalinity. The
pair of unsharedelectrons of the nitrogen atom is the key to the
properties. Amines are weak bases, with protonation occur-
ring in the acidic and moderately alkaline pH range.
solubilization in water. Acetic acid is usually employed in
amines neutralization. The neutralization degree of amines
used in flotation is variable and is generallybetween 20% and
75% (Hukki and Vartiainen, 1953).
Fatty amines are the product of fatty acids amonolysis. The
reaction produces primary amines with the chain length asso-
ciated with the different mixtures of compounds used. The
primary fatty amines with chain lengths of 16C or more
present low activity in the liquidlair interface, and they are
usually used together with a frother (Ducker et al., 1989).
w h e n an alcohol is reacted with acrvlonitrile and then
reduced, the result is an amine with anoxygen atomin its chain
(etheramine). The oxygen confers a partially hydrophilic
character to the hydrophobic chain; the result is an amine with
higher solubility .~~hektheramines present usually good froth-
ing action and a specific frother is not required in many
systems. A second contact of an ether with acrylonitrile
~ r o d u c e san ether diarnine (Scott and Smith, 199 1).
A condensate amine is thk reaction product of a polyamine
with an organic acid. The polyamines are short-chain com-
pounds, and the acid is frequently a tall oil (fatty acids mixture
produced from pinus Elliot).
Condensate: R-C-NH-C-C-NH-C-C-NH-C-R (1 )
// \\
0 0
The current value of pellet-feed fines concentrates in the
international market is very low, and the search for less-

Nonmeeting paper number 99-342. Original manuscript submitted for review July 1999. Revised manuscript accepted for
publication December 1999. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME
prior to Aug. 31, 2001.

MINERALS 8 METALLURGICAL PROCESSING 5 VOL. 10, NO. 1 FEBRUARY 2001

 - - -
1 Table 1 - Characteristics of the arnines under investigation.
Molecular Density, Alkyl Neutralization
Trade name Manufacturer Description weight glcm3 groups degree

1 Flotigam
SA-B
Clariant fatty stearyl
amine acetate
317 to 363 0.9 C14-15%
C16-20%
(21865%
-

Flotigam Clariant fatty tallow 33 to 345 0.9 C14-5% -

T2A-B arnine propylene C16-30%
(paste) c18-65%
Collector Clariant fatty diarnine - - - -
075194 propulene
(paste)
HOE F2835-B Clariant ether diamine acetate - - C12-13 50%

Flotigarn Clariant etheramine acetate -

EDA-B

Flotigam Clariant etherarnine acetate -

EDA-3B

MG-70-A5 Sherex etherarnine acetate 254 0.89 C18- 5%-15%

(coarse silica)' 10 alcoxi -

MG-83-A Sherex ether diamine acetate 193 0.923 - -

MG-98-A3 Sherex etheramine acetate 239 0.85 propamine 35%-12%

(silica slimes)' isodecyloxi

ECAN 04D Pietschemicals etherarnine - - C12-C13 partial

I Nb 104 Pietschemicals condensate - - C18 -

Nb 112 Pietschemicals condensate - - arnine C8-10 -
condensate C18
/ Colmin C1Z Ouimikao etheramine acetate - - - 30%

I1 A-3
Akzo

*Supplier'ssuggestion
etheramine acetate - - - -

expensive reagents is, therefore, necessary. On the other
hand, the production of concentrates with low impurity
contents and high iron grades, at adequate recovery levels,
requires the use of reagents that present effective perfor-
mance. The reagents utilized in the cationic flotation of iron
ores are amine, starch and caustic soda. In Brazilian concen-
trators, high-purity starches were replaced by locally manu-
factured, less pure products having alower cost, adiversity of
suppliers and with an equivalent performance (Viana and
Souza. 1988).
Amines from several classes, supplied by different manu-
facturers, are available in the Brazilian market. Some manu-
facturers do not present complete technical data of their
products. But infrared spectrometry is a powerful tool for the
identification of the class of amine compound present in a
flotation reagent and for detecting the presence of impurities.
Using infrared spectrometry, this investigation character-
ized the commercial amines available in the Brazilian mining-
chemicals market. The investigation then tested the flotation
performance of each amine that was analyzed.
Experimental methods
Reagents. The amines utilized are listed in Table 1 . A 99%-
pure (dry basis) conventional starch, consisting of 75% amy-
lopectin and 25% amylopectin, was employed as iron oxides
depressant in all flotation experiments.
Mineral sample. An itabirite sample assaying 54.2% Fe and
20.4% S i 0 2 was utilized in all flotation experiments. A
mineralogical investigation indicated 98% S i 0 2 liberation in
the < 149-pn size range
Equipment. A Fourier transform infrared spectrometer, Perkin
Elmer FT-IR 1760X controlled through an interface con-
nected to a Professional Computer Perkin-Elmer 7700, was
used in the reagents characterization stage. Bench-scale flota-
tion experiments were carried out in a modified laboratory
Denver flotation cell.
Methods. Analyses by infrared spectrometry (transmission
method) were performed with the objective of identifying in
detail the amines under investigation. The liquid amines and
the light pastes were introduced in the spectrometer without
previous preparation. However, in the case of the dark paste
it was necessary to make a pressed KBr tablet before the
analysis. Absorption spectra were recorded for all the amines.
The flotation experiments were carried out under the fol-
lowing conditions: 3-L cell volume, 1,400-rpm rotor speed,
pH 10, five-minute conditioning time and 20% solids
The flotation experiments were performed according to a
two levels full factorial design (Box et al., 1978; Montgomery,
1991). The decision of keeping pH, conditioning time and
percent solids at constant levels was based on exploratory

FEBRUARY 2001 VOL. 18 NO. 1 MINERALS 8 METALLURGICAL PROCESSING

experiments. The test work was divided
into four series involving the following
variables :

ether monoamines and starch con-

centrations,
ether diamines and starch concen-
trations,
ether amines of different neutral-
ization degrees and starch concen-
trations and
three kinds of amines and starch Figure 1 -Transmission infrared spectrum of the rnonoetheramine acetate 30%
concentrations. neutralized Flotigam EDA-36.

Results and discussion loo

Characterization. The recorded spectra (a)
for all commercial etheramine acetates
and reference compounds are very simi-
lar, an indication of the purity of the
commercial reagents. The spectrum for
EDA-3B (etheramine acetate 30% neu-
g 95
tralized) is presented in Fig. 1. The out-
standing features of this spectrum are:
m
rr
a broad peak at approximately 3,400 2
cm-', due to NH, stretching vibra- +Condensate Nb 112
tions; +Fatty amine Flotigam SA-B
a group of sharp and strong peaks in
the 3,000- to 2,700-em-' range, due *Ether monoamine ECAN 04D
to stretching vibrations of the CH,
85 I . . ' . I ' . . . I . ' . m I . ~ ' . I ' ' " ~ ' ' ' '
and CH3groups of the hydrocarbon
35 40 45 50 55 60 65
chains;
a very broad and strong band in the Amine concentration (g/t)
3,600- to 2,300-cm-I range, due to 35
the stretching vibrations of the NH3+
group, known as the "ammonium
peak" and diagnostic of monoam-
30 -
ine and diamine primary salts;
a broad peak at 2,180 cm-', due to
an unspecified band associated to
the NH, group;
and
peaks1,200
in the
ern-',
region
duebetween
to bending
1,800
brations of the NH,, CH, and CH,
groups and also acetate ions (this
vi-
-
g 20
$ 15 i
25

10
(b) 1 -+Condensate
+Fatty
*Ether
Nb 112
amine Flotigam SA-B
monoamine ECAN 04D
region is diagnostic of etheramines): -
and
sharp and strong band at 1,114 cm-
', due to the C-0-C (this band is
diagnostic of this group).

The spectra of three fatty amine ac-

5 35 40 45

Amine concentration (glt)

50 55 60 65

etates are very amongthemse1ves3 Figure 2- (a) Iron recovery and (b) silica content in the concentrate asa function
suggesting the purity of the ~ ~ m n e r c l a l of amine concentration for three kinds of arnines.
reagents. The main diagnostic feature with
respect to etheramines is the absence of bands in the 1,800- to 1,500-cm-l range, which are
the ether band at 1,l 14 cm-l. sharper than in the case of other amine related com-
The spectra of amine condensates are distinct from those of pounds, due to the stretching vibration of the carbonyl
etheramines and fatty amines. Their main features are: and its influence on the vibrations occurring in this
range.
-
a sham andmedium-strong veak in the 3.500- to 3.000-
&

cm-' range and a peak near 39100 cm-l$duelo No distinctive spectral differences were found between the
NH, stretching vibrations modified by the effect of the diamines (in all forms and derivatives) and the equivalent
carbonyl in the amide group; and monoamine compound.

MINERALS 8 METALLURGICAL PROCESSING 7 VOL. 18, NO. 1 . FEBRUARY 2001

1 Table 2 - Metallurqical balance of the tests with ether monoamine acetate 3O0I0neutralized EDA-3B. I
Grade Recovery
Mass recovery,

I Test
Amine Starch Product

Tailings
70 Fe, % SiO,, % Fe, %

Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Tailings
Concentrate
Calc. feed

Flotation. A large number of rougher only bench-scale tlota-
tion experiments proved that fatty amines and amine conden-
sates yield concentrates with silica contents much higher than
acceptable (Fig. 2). On the other hand, etheramines (monoam-
ines i n d diamines) are by far more-effective collectors for this
system. The presence of the hydrophilic O(CH2I3 group
improves the solubility of the reagent, facilitating its access to
the solid-liquid and liquid-gas interfaces. It also enhances the
elasticity of the liquih film around the bubbles, imparting
excellent frothing characteristics. Fatty amines and conden-
sates align themselves as solid monolayers in the film. result-
ing in brittle froths and low quartz recovery.
Presenting mass balances and grade vs. recovery curves for
all flotation tests would be tedious. Figure 2 illustrates iron
recovery and silica content as a function of amine concentra-
tion for three collectors representing each class of reagent.
The superiority of the etheramine regarding the main crite-
rion, silica content in the concentrate, is clear.
The metallurgical balances of the tests with Flotigam
EDA-3B are presented in Table 2. This reagent is by far the
most common quartz collector in Brazilian concentrators.
The lowest silica content in the concentrate criterion was
used again for comparing the performance of the 14 collec-
tors under investigation, Test conditions and metallurgical
parameters (Fe and S i 0 2 grades and Fe recovery) are pre-
sented in Table 3. For the ore sample utilized in the present
investigation, ether monoamines proved to be more efficient
quartz collectors than diamines. On the other hand, diamines
substitute for monoamines in another Brazilian concentrator
whenever concentrates with lower silica contents are re-
quired.
Conclusions
For the ore under investigation, ether monoamines proved to
be more efficient collectors than ether diamines.
Fatty amines and condensates are poor collectors in the
cationic flotation of quartz from iron ores.
Etheramines show a characteristic and well-defined peak,
due to the C - 0 group, that differentiates them from the other
classes. The distinction betweencondensates and fatty amines
is also possible by infrared spectrometry. This technique does
not differentiate monoamines from diamines.
References
Box, G.E., Hunter, W.G., and Hunter, J.S., 1978, Statistics forExperiments, 2"a
Ed., John Wiley, New York, 539 pp.
Ducker, W.A., Pashley, R.M., and Ninham, B.W., 1989, "The flotationof quartz
using a double-chained cationic surfactant," Journal of Colloid Interface
science, VOI. 128, NO. 1 , p. 66-77.
Dudenhov, S.V., Shubov, L.V., and Glasunov, L.A., 1980, Fundamentos de la
Teoria y la Practica de Empleo de Reactivos de Flotation, MIR, Moscow,
404 pp. (in Spanish)

FEBRUARY 2001 VOL. 18 NO. 1 8 MINERALS 8 METALLURGICAL PROCESSING

 Table 3 - Metallurgicalbalances of the bench scale flotation experiments of an itabirite ore yielding the lowest silica content
for each amine under investigation
Grade Recovery
Collector, Starch,
Collector Slit s/t Product Fe, % SiO,, % Fe, %

Flotigam SA-B 60 500 Tailings 9.00 85.13 3.87

fatty Concentrate 58.25 20.25 96.13
Calc. feed 48.08 33.65 100.00

Flotigam T2A-B 60 500 Tailings 8.70 86.71 2.03

fatty Concentrate 5 1.70 24.91 97.97
Calc. feed 46.98 31.69 100.00

Collector 075194 60 500 Tailings 14.10 79.79 4.68

fatty diamine Concentrate 54.21 21.25 95.32
Calc. feed 47.84 30.55 100.00

HOE F 28358 50 400 Tailings 12.76 81.04 9.39

ether diamine Concentrate 66.80 03.09 90.61
Calc. feed 47.80 30.50 100.00

Flotigam EDA B 60 500 Tailings 14.20 81.24 11.48

ether monoamine Concentrate 64.20 05.02 88.52
Calc. feed 45.72 33.19 100.00

Flotigam EDA-3B 60 1,000 Tailings 10.51 84.42 08.54

ether monoamine Concentrate 67.61 02.10 91.46
Calc. feed 46.18 33.00 100.00

MG 70-A5 60 500 Tailings 12.23 81.25 9.87

ether monoamine Concentrate 64.20 07.01 90.13
Calc. feed 45.23 34.10 100.00

MG 83-A 60 500 Tailings 14.80 87.40 10.33

ether diamine Concentrate 64.90 05.70 89.67
Calc. feed 48.08 33.13 100.00

Mg 98-A3 60 500 Tailings 14.10 79.79 8.52

ether monoamine Concentrate 65.20 06.70 91.48
Calc. feed 49.82 28.70 100.00

ECAN 04D 60 500 Tailings 09.00 83.82 07.68

ether monoamine Concentrate 68.91 1.26 92.32
Calc. feed 45.61 33.88 100.00

Nb104 50 400 Tailings 50.72 24.42 1.66

condensate Concentrate 47.02 31.90 98.34
Calc. feed 47.08 31.78 100.00

Nb112 60 500 Tailings 14.25 78.82 4.59

condensate + amine Concentrate 52.41 24.12 95.41
Calc. feed 46.68 32.34 100.00

Colmin C12 40 600 Tailings 10.80 84.97 4.72

ether monoamine Concentrate 66.40 4.22 95.28
Calc. feed 53.43 23.06 100.00

Poliad A-3 40 600 Tailings 8.06 86.04

ether monoamine Concentrate 67.30 2.48 93.54
Calc. feed 46.70 31.80 100.00

Hukki, R.T., and Vartiainen, O., 1953, "An investigation of the collecting effect
of fatty acids tall oil on oxide minerals, particularly on ilmenite," Mining
Engineering, pp. 81 8-820.
Montgomery, D.C., 1991, Design and Analysis of Experiments, 2naEd.. John
Wiley, New York, 532 pp.
Scott, J.L., and Smith, R.W., 1991, "Diamine flotation of quartz," Minerals
Engineering, Vol. 4, No. 2 , pp. 141-150.
Viana, P.R.M., and Souza, H.S., 1988, "The use of corn grits as a depressant
for the flotation of quartz in hematite ore," Froth Flotation, Developments in
Mineral Processing 9, Elsevier, Amsterdam, pp. 233-244.

MINERALS & METALLURGICAL PROCESSING VOL. 18, NO. 1 FEBRUARY 2001