Minerals Engineering 111 (2017) 198–200

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Short communication

Use of wood hemicelluloses to improve copper recovery from high clay Cu- MARK
Mo ores
⁎
Vicente A. Hernandeza, , Alvaro Ulloab, Leopoldo Gutierrezb
a
Biotechnology Center, University of Concepcion, Barrio Universitario S/N, Concepción, Chile
b
Department of Metallurgical Engineering, University of Concepcion, Chile

A R T I C L E I N F O A B S T R A C T

Keywords: This work was aimed at studying the effect of wood galactoglucomannan hemicelluloses (HC) on the recovery of
Wood hemicelluloses copper and molybdenum from a high clay ore. The performance of HC was compared with the results obtained
Galactoglucomannan using carboxymethyl cellulose (CMC). Results indicated that HC has a stronger effect than CMC to increase the
Flotation recovery of Cu from a high clay ore, but a higher depressing effect on the recovery of Mo. At 230 ppm of HC
Copper sulphide flotation
copper recovery increases 7.6 percentage points and Mo recovery decreased 20.7 percentage points respect to
Carboxymethyl cellulose
samples floated without HC. Thus the use of HC and CMC to improve copper recovery in the flotation high clay
copper ore appears to be very promising, but considerations must be done when treating molybdenum rich ores.
Due to the fact that HC are semi-amorphous with side hydroxy group on the chain, one possible mechanism of
adsorption may be related to hydrogen bonds existing between these hydroxy groups and the surfaces of the clay
mineral particles. Further studies that include tests to clarify the mechanisms of adsorption of HC on clay mi-
nerals and valuable species, as well as the effect of this reagent on other types of high clay ores are necessary in
the future.

1. Introduction
Carbohydrates such as dextrin, starch, and celluloses have been
proposed as dispersing agents for clays in the flotation of potash,
phosphates and iron ores (Leja, 1982; Bulatovic, 2007). The biode-
gradable nature of these compounds allow their use and safe rejection
in the flotation tailings with no environmental restrictions (Leja, 1982;
Pugh, 1989). In copper sulphide ores processing, the presence of clay
minerals is problematic in flotation circuits (Uribe et al., 2016). How-
ever, studies on the dispersing effect of carbohydrates in the process of
flotation of high clay copper ores are scarce.
A potential source of carbohydrates can be found in forest products
such as wood cellulose which reached a worldwide production of 117
million tons in 2015 (Forest products statistic, FAO, 2017). For ex-
ample, sodium carboxymethyl cellulose (CMC) is a well-known dis-
persant agent used to reduce the negative effect of slimes in the flota-
tion process of several minerals (Jardeby et al., 2005; Bulatovic, 2007).
Besides, it is known that wood is also rich in hemicelluloses (HC)
(Timell, 1964), which were previously proposed by Lewis and Panzer
(1989) as effective dispersing agents in the flotation of a wide range of
mineral resources including copper ores. However, neither data nor
examples of the effect of HC on the flotation of high clay copper ores
were reported by these authors. Nowadays, HC, lignin and other wood
byproducts, are extracted together and burned for power generation
purposes in the process of cellulose production (Helmerius et al., 2010).
Unlike CMC, that requires to be synthesized from soluble cellulose, HC
production only requires an extraction process using hot water (Reyes
et al., 2013). This represents an advantage as its production leads to low
operational costs.
The objective of this research work was to assess the effect of wood
galactoglucomannan HC on the recovery of copper and molybdenum
from a high clay ore. The performance of HC was compared with the
results obtained using CMC.
2. Materials and methods
2.1. Samples and reagents
The study was carried out using a Cu-Mo ore sample obtained from
a mine located in Northern Chile. The chemical analysis of this sample
indicated a composition of 0.49% Cu, 0.014% Mo and 5.93% Fe. XRD
analyses were carried out using a Bruker D4-Endeavor operated with
Ni-filtered Cu radiation which showed that the main copper sulphides
were chalcopyrite, chalcocite and covellite. The analysis also indicated

⁎
Corresponding author.
E-mail address: vhernandezc@udec.cl (V.A. Hernandez).

http://dx.doi.org/10.1016/j.mineng.2017.06.023
Received 15 March 2017; Received in revised form 7 June 2017; Accepted 26 June 2017
0892-6875/ © 2017 Elsevier Ltd. All rights reserved.
V.A. Hernandez et al.
that kaolinite concentration in the sample was around 13%.
HC samples of 44.000 g/mol MW extracted from softwood chips
according to the method proposed by Reyes et al. (2013) were provided
by the Laboratory of Renewable Resources (LRR) of the University of
Concepción. Technical grade CMC of 90.000 g/mol MW was obtained
from Sigma-Aldrich.
2.2. Procedures
The flotation tests were done using a 2.7 L Denver Flotation ma-
chine. The flotation feed of 1 kg used in these experiments was pre-
viously ground in a laboratory ball mill to a P80 of 150 µm, and then
placed in the flotation cell where the solids content was adjusted to
30% by weight. Then the pH was adjusted to 9 using lime and the slurry
was conditioned for 2 min at 900 rpm. At this time HC or CMC were
added at varying concentrations (0, 115, 230 and 450 ppm). It has to be
noted that these reagents were prepared by dissolving the reagents 12 h
in hot water previous to the experiments. Finally, collectors AERO 7156
(42 g/t) and 3753 (30 g/t), and frothers MB-78 (25 g/t) and MIBC (5 g/
t) were added and conditioned for 1 min. The flotation tests were done
using an air injection of 9 L/min and samples of the concentrates were
collected during 8 min by scraping the froth out manually every 10 s.
Concentrates and tailings were then analyzed for Cu and Mo to de-
termine the recoveries and grades. All the tests were done in duplicates
with an average standard deviation of 0.8 percentage points.
3. Results
Fig. 1 shows the Cu and Mo recoveries obtained in the flotation tests
at different dosages of galactoglucomannan HC. It can be seen that the
use of HC generates a positive effect in the recovery of copper over the
whole range of dosages tested in this work. Copper recovery reaches a
maximum value of 86% at a dosage of 230 ppm of HC, which represents
an increase of 7.6 percentage points respect to the tests without HC. At
the same time the copper grade increases to 3.2% at 230 ppm HC which
also indicate a positive effect on the quality of the concentrate. In
contrast, the experimental data indicate that Mo recovery steadily de-
creases as the dosage of HC increases. At 230 ppm of HC, Mo recovery
decreased 20.7 percentage points respect to samples floated without
HC. This result suggests that the use of HC in the process of flotation of
high clay ores could be useful as long as the ores do not contain Mo.
For comparison purposes, flotation tests to evaluate the effect of
CMC were also performed. Fig. 2 shows the Cu and Mo recoveries ob-
tained as a function of the CMC dosage. It can be seen that Cu recovery
is higher in the presence of CMC at all the dosages tested, although, no
major differences were observed at the different concentrations used.
199
Minerals Engineering 111 (2017) 198–200
The highest increment of Cu recovery was of 3.5 percentage points at
155 ppm of CMC, which is lower than that observed using HC. The
copper grade increased to 2.4% at 155 ppm CMC which is also lower
than it was obtained using HC. Similar to HC, CMC also had a negative
impact in molybdenum recovery which is a trend that was previously
reported for other polymers such as dextrin and flocculants (Wie and
Fuerstenau, 1974; Laskowski and Castro, 1999).
4. Discussion
The adverse effect of clay minerals on the flotation process of copper
sulphide ores can be explained by several mechanisms (Fornasiero and
Ralston, 2005; Uribe et al., 2016). The most widely proposed me-
chanism is slime coating, which consists in the deposition of colloidal
clay particles on the surfaces of larger particles of valuable minerals
that were previously hydrophobized by collectors. As a result a hy-
drophilic layer is created and the efficiency of the flotation process is
reduced. The presence of clay minerals also changes the rheological
behavior of suspensions which influences the efficiency of several im-
portant flotation sub-processes, i.e., bubble rise velocity, particle-
bubble collision, attachment and detachment, and froth mobility
(Hoffman, 1992). Another phenomena such as changes of froth stability
(Pugh, 1996), reagents up-take (Ndlovu et al., 2013) and coating of
bubbles with clay particles (Uribe et al., 2016) were also proposed to
explain the negative effect of clay minerals on the process of flotation.
The experimental results of copper recovery presented in Figs. 1 and 2
indicate that the use of HC and CMC generates a positive effect in the
recovery of copper over the whole range of dosages studied with re-
covery increments up to 7.6 percentage points respect of samples
without reagents. At the same time the copper grade in the concentrate
increases. The explanation of these results may be related to the action
of these reagents on the five previously explained mechanisms. Pre-
vious studies showed that CMC has a strong dispersing effect on several
mineral systems (Arinaitwe, 2013) through adsorption on clay minerals
generating dispersing conditions that have a positive effect on the
process of flotation. The results obtained in this work regarding to the
effect of HC suggests a similar dispersing effect, but according to the
data collected, HC seems to have a slightly stronger impact than CMC.
Hemicelluloses are heterogeneous polysaccharides with degrees of
polymerization that are rather low reaching average values of around
200. Hemicellulose molecules are semi-amorphous with side hydroxy
group on the chain molecule (Pettersen, 1984), which may explain the
interactions with clay mineral particles. It is possible that the adsorp-
tion mechanism may be related to hydrogen bonds existing between the
hydroxy groups and the surfaces of the clay mineral particles. The ad-
sorption mechanisms have to be further studied. The data also indicate
Fig. 1. Copper and molybdenum recoveries obtained in the flotation tests
done at different dosages of galactoglucomannan hemicellulose (HC).
Copper and Molybdenum grades are shown for each case, respectively.
V.A. Hernandez et al.
that the use of HC decreases the recovery of molybdenum. Previous
studies showed that the flotability of molybdenite is negatively affected
by polysaccharides such as dextrin and CMC (Wie and Fuerstenau,
1974). The results obtained in this work indicate that HC may have a
similar effect. The use of HC and CMC to improve copper recovery in
the flotation high clay copper ore appears to be very promising, but
considerations must be done when treating molybdenum rich ores.
Although the effect of CMC is rather similar to the effect of HC, the
latter reagent has the advantage that can be used right after extracted
and purified from wood chips and fibers (Reyes et al., 2013). In con-
trast, CMC is synthesized from soluble cellulose which requires a more
complicated process of production. Thus, in term of cost of production
the use of HC in flotation of high clay copper ore appears more con-
venient than CMC. In addition, the biodegradable nature and avail-
ability of wood HC offer environmental advantages that can improve
the sustainability of copper processing, lowering the toxicity of flota-
tion tailings.
Further research must be conducted to confirm the results obtained
in this work. Such experiments might include studies to clarify the
mechanisms of adsorption of HC on clay and valuable species, and the
effect of this reagent in other types of high clay ores.
5. Conclusions
The ability of HC to improve copper recovery in the flotation of a
high clay Cu-Mo ore was tested and compared to CMC. Results in-
dicated that HC has a stronger effect than CMC to increase the recovery
of Cu from a high clay ore, but it also has a higher depressing effect on
the recovery of Mo. Thus, the use of HC appears advisable only when
processing high clay copper ores with no presence of molybdenite. The
promissory results obtained in this work need to be confirmed by fur-
ther studies, which might include tests to clarify the mechanisms of
adsorption of HC on clay and valuable species, and the effect of this
reagent in other types of high clay ores.
Acknowledgements
This work was supported by “Convenio de Desempeño, UCO 1302”,
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Minerals Engineering 111 (2017) 198–200
Fig. 2. Copper and molybdenum recoveries obtained in the flotation tests
done at different dosages of carboxymethyl cellulose (CMC). Copper and
Molybdenum grades are shown for each case, respectively.
Ministry of Education, Chile. Leopoldo Gutierrez thanks the support
from FONDECYT under the projects initiation into research no.
11140184, and Centro CRHIAM-Fondap no. 15130015.
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