minerals

Article
A New Collector for Effectively Increasing Recovery
in Copper Oxide Ore-Staged Flotation
Renfeng Zhu *, Guohua Gu, Zhixiang Chen, Yanhong Wang and Siyu Song
School of Minerals Processing and Bio-Engineering, Central South University, Changsha 410083, China;
guguohua@163.com (G.G.); chenzhixiang93@163.com (Z.C.); yanhong.wang@csu.edu.cn (Y.W.);
165612115@csu.edu.cn (S.S.)
* Correspondence: nicky-xiaozhu@163.com; Tel.: +86-0731-8883-0960




Received: 11 September 2019; Accepted: 27 September 2019; Published: 29 September 2019


Abstract: A new method, staged flotation for effectively increasing the recovery of ultra-fine copper
oxide ore with a new type of collector (ZH-1, C3-5 carbon chain xanthate) is proposed for the first time.
The flotation process and mechanism were examined by flotation tests, entrainment rate analysis,
laser particle size experiments and microscopic imagery as well as economic feasibility analysis.
It was demonstrated that the collector isoamyl sodium xanthate (ISX) shows a good collection ability
(recovery exceeded 95%) for azurite, but the recovery was relatively much lower for malachite
(only near 80%) due to the different particle size distribution. The new type of xanthate ZH-1 has
shown a high-efficiency collection performance for fine-grained malachite. The recovery achieved
for −10 µm malachite was more than 95% when the ZH-1 dosage was 150 mg/L, while the average
particle size of −10 µm malachite sharply increased from 4.641 µm to 9.631 µm. The batch flotation
results indicated that the copper oxide flotation recovery increased from 79.67% to 83.38%, and the
grade also raised from 18.08% to 18.14% after using the staged flotation technology with ZH-1 as
collector during the flotation of −25 µm ore. It was confirmed that this technology was quite effective
for the recovery of copper oxide at the Dishui Copper Processing Plant, which successfully increased
its gross profit by 1.6 million US$ per year.

Keywords: staged flotation; malachite; azurite; fine-grained; mixed xanthate; flocculation

1. Introduction
In order to improve the utilization rate of copper oxide ore resources, it is necessary to finely grind
it for achieving liberation of as much as possible due to the fine inlay size of the valuable minerals,
including malachite and azurite [1–6]. However, as particle size decreases, the flotation behavior of
copper oxide mineral particles undergoes many changes. For instance, the fine-grained copper oxide
ore is poorly floatable and displays a lower recovery during the flotation process [7]. Up to now,
sulfide flotation is still one of the most widely used processes in copper oxide ore dressing, but it is
unable to solve the problem of low recovery of micro-fine oxidized copper ores [8,9]. According to
statistics, about one sixth of the copper resource is lost to tailing ascribed to fine particles that cannot
be effectively recovered [10,11]. Therefore, how to improve the flotation vulcanization efficiency of
fine-grained copper oxide ore has an important role in meeting the market’s growing demand for
copper, and it is also significant for the conservation of mineral resources.
The Dishui Copper Processing Plant is located in Qarqi Town (Aksu Prefecture, Xinjiang Province,
China). The mining area is about 21 square kilometers, with the copper grade more than 1%, and the
production scale is 3000 tons per day. The embedded granularity of the useful minerals, such as
malachite and azurite, is not uniform in the copper ore. Therefore, it is difficult to determine the best
grinding fines in a section of grinding since too much fineness will generate over-grinding which

Minerals 2019, 9, 595; doi:10.3390/min9100595 www.mdpi.com/journal/minerals

Minerals 2019, 9, 595 2 of 13

eventually worsen the flotation process, but too low fineness will cause part of the copper minerals
to be difficult to dissociate completely, and undissociated minerals cannot be recovered by flotation.
At present, the on-site control grinding fineness of Dishui Copper Processing Plant is about 90%.
The multi-sampled and sieved grinding products show that the +74 µm copper grade is the highest,
generally above 0.30%, but the −25 µm slime content is more than 60%, which not only causes a waste of
the flotation reagent, but also deteriorates flotation indicators. The fine-grained particles possess three
main characteristics, including small mass, large specific surface area and high surface energy [12–14].
It is difficult to overcome the energy barriers between the ore particles and the bubbles then adhere to
the surface of the bubbles. Besides, the large specific surface area and high surface energy cause severe
non-selective agglomeration between the gangue particles and the valuable particles, resulting in a
larger amount of reagent consumption during the flotation process and a decreasing in the selectivity
of reagent adsorption [14–17].
Against this background, we proposed that the idea of stage treatment in the beginning,
which including employing leaching or combination of metallurgy to dispose the −25 µm slime
that separated from the grinding product by screening, and other −74 ~ +25 µm particles were treated
by a conventional flotation process. In this way, the consumption of reagents can be greatly reduced
during the flotation of +25 µm ore, especially the amount of xanthate collector. In our follow-up
research, we conducted an acid leaching and ammonia leaching experiment on −25 µm products.
However, the results showed that there are still many problems that cannot be solved in the application
of this method. For example, consumption of a large amount of acid during the acid leaching process,
the separation problems between solid and liquid and lowing leaching rate (only about 75%). On the
other hand, the ammonia leaching effect is better than that of acid leaching, and the recovery of
copper is about 85%. However, it also has the same problem of large consumption of chemicals,
more seriously, ammonia volatilization during the leaching process will have a great harmful impact
on the environment protection. Part of −25 µm slime could not be effectively treated and was stranded
for a long time. Chen et al. [16] have shown that it is possible to increase the size of the fine particles
by performing flocculation between particles, which enables the effective recovery of fine-grained
minerals. The selective flocculation process was to add a polymer collector to the slurry after slurry
adjustment, and selectively flocculated the target mineral under the action of shearing field, and then
used flotation, re-election or de-sludge processes to achieve the separation of target minerals.
In this paper, we have designed a new type of collector, ZH-1, with excellent flocculation selectivity
and collecting capacity for −25 µm valuable minerals, and finally improved the flotation recovery
for this fraction of malachite. The mechanism of action between ZH-1 and mineral was studied by
flotation kinetics, entrainment rate calculation, laser particle size analysis and microscopic imaging
analysis. In addition, locked-cycle tests of grading flotation and economic feasibility calculation were
carried out in this research, aiming to further verify the feasibility of the technical scheme and increase
the recovery of copper oxide, meanwhile improving the utilization of mineral resources.

2. Materials and Methods

2.1. Materials
Pure malachite, azurite and industrial samples were obtained from the Dishui Copper Processing
Plant, Qarqi, Xingjiang, China. The purity of the mineral sample was more than 90% by X-ray diffraction
analysis, as shown in Figure 1. The chemical analysis results of the practical sample were listed in
Table 1. Hand-selected crystals of these minerals were crushed to −1 mm in a laboratory roll crusher.
The crushed products were then ground in a ceramic ball mill and the product was screened into three
narrow size fractions: −38 + 25 µm, −25 + 10 µm, and −10 µm. The size distribution of narrow size
fractions is summarized in Table 2.
Minerals 2019, 9, 595 3 of 13
Minerals 2019, 9, x FOR PEER REVIEW 3 of 13

(a) (b)
Figure 1. X-ray
X-ray diffraction
diffraction (XRD) spectra of pure (a) Azurite and (b) Malachite for tests.

1. Chemical
Table 1.
Table Chemical analysis
analysis results
results of
of practical
practical samples.
samples.
ElementAzurite
Element AzuriteMalachite
Malachite Chalcocite
Chalcocite Limonite
Limonite Ilmenite
IlmenitePyrite Pyrite
Rutile Rutile
Content/%
Content/% 0.72 0.72 0.590.59 0.22 0.730.73 0.35 0.35 0.30 0.30 0.25 0.25
Element Calcite quartz plagioclase muscovite chlorite dolomite others
Element Calcite quartz plagioclase muscovite chlorite dolomite others
Content/%
Content/% 24.9324.93 22.83
22.83 15.25
15.25 9.889.88 9.51 9.51 7.53 7.53 6.91 6.91

Table 2. The size distribution of narrow size fractions.

Table 2. The size distribution of narrow size fractions.
Size Fraction/µm d90/µm Mean Size/µm
Size Fraction/µm d90 /µm Mean Size/µm
−38 + 25 34.876 33.213
10 + 25
−25 + −38 34.876
23.454 33.213 22.647
−10−25 + 10 23.454
8.535 22.647 6.375
−10 8.535 6.375
The new type of collector, ZH-1, is based on mixed xanthates (3–5 carbon chain lengths) in a
certain
Theratio. It was
new type suppliedZH-1,
of collector, by the Institute
is based of Multipurpose
on mixed xanthates (3–5 Utilization
carbon chainof lengths)
Mineral in Resources
a certain
Flotation
ratio. Reagents
It was Limited
supplied by theCompany,
InstituteGuangzhou, China.Utilization
of Multipurpose The solution was made
of Mineral up to theFlotation
Resources required
volume by
Reagents adding
Limited distilledGuangzhou,
Company, water and China. then left
Theto equilibrate
solution overnight.
was made Fresh
up to the solutions
required volumewere
by
prepared
adding every three
distilled waterdays. In the
and then leftflotation tests, overnight.
to equilibrate ZH-1 or isoamyl sodium xanthate
Fresh solutions (ISX) or
were prepared isopentyl
every three
potassium
days. In thexanthate
flotation (IPX) was used
tests, ZH-1 as thesodium
or isoamyl collectors, ammonium
xanthate sulfate and
(ISX) or isopentyl ethylenediamine
potassium xanthate
phosphate
(IPX) (ASEP)
was used as were used as activators.
the collectors, ammonium Sodium sulfide
sulfate and methyl isobutyl
and ethylenediamine carbinol (ASEP)
phosphate (MIBC) were
vulcanizingSodium
used as activators. and foaming
sulfideagent, respectively.
and methyl isobutylWater glass
carbinol was used
(MIBC) wereasused
dispersing agent inand
as vulcanizing the
closed-circuit flotation process. Hydrochloric acid (HCl) and sodium hydroxide (NaOH)
foaming agent, respectively. Water glass was used as dispersing agent in the closed-circuit flotation were used
as the pH
process. regulators. acid
Hydrochloric In addition,
(HCl) and allsodium
reagents used in (NaOH)
hydroxide flotation were
tests used
wereasofthe analytical grade.
pH regulators.
Deionized
In addition,distilled water
all reagents wasinused
used for micro-flotation,
flotation microscopic
tests were of analytical imaging
grade. tests,distilled
Deionized and laser particle
water was
size analysis.
used for micro-flotation, microscopic imaging tests, and laser particle size analysis.

2.2. Methods

2.2.1. Micro-Flotation Tests

2.2.1. Micro-Flotation Tests
A
A XFG-1600
XFG-1600 type
type (mechanical agitation) flotation
(mechanical agitation) flotation machine
machine (Hongxing
(Hongxing mine
mine machinery
machinery factory,
factory,
Luoyang, China) with
Luoyang, China) with the
the volume
volume of of 40
40 mL
mL waswas used
used in
in the
the micro-flotation
micro-flotation tests.
tests. The
The mineral
mineral
suspension
suspension was prepared by adding 2.0 g of a single mineral (−74 um) to 40 mL of solutions in single
was prepared by adding 2.0 g of a single mineral (−74 um) to 40 mL of solutions in single
mineral flotationtests.
mineral flotation tests.The
The
pHpH of of
thethe mineral
mineral suspension
suspension waswas adjusted
adjusted to thetodesired
the desired operating
operating value
value
by adding HCl or NaOH stock solutions. Flotation concentrates were then collected for a totaltotal
by adding HCl or NaOH stock solutions. Flotation concentrates were then collected for a of 5
of 5 min.
min. In flotation
In flotation dynamics
dynamics tests
tests of of malachite,
malachite, the general
the general reagentreagent addition
addition schemescheme involved
involved ASEP,
sodium sulfide and collector ZH-1 or ISX, then MIBC frother addition with each stage having a 2-min
Minerals 2019, 9, 595 4 of 13

ASEP, sodium sulfide and collector ZH-1 or ISX, then MIBC frother addition with each stage having
a 2-min conditioning periods prior to the addition of the next reagent. Concentrates were collected
5 min flotation time with a scraping rate of every 2 s. The following conditions were constant in all
tests, unless otherwise noted: (1) a superficial gas velocity 3.11 cm/s, (2) impeller rotational speed of
1900 rpm, (3) solids concentration of 4.7%, (4) frother addition of 20 mg/L at the beginning of the test,
(5) a froth depth of about 0.5 cm. In single mineral flotation, the recovery was calculated based on solid
weight distribution between the two products. Product wet and dry weights were used to determine
the water recovery.

2.2.2. Recovery by Entrainment

Particles were recovered via two primary mechanisms: (1) by true flotation, in which hydrophobic
particles were recovered by attachment to air bubbles, and (2) by entrainment, which involves
the nonselective recovery of particles in water to the concentrate, irrespective of whether they are
hydrophobic or hydrophilic [18–20]. It is worth noting that the water in the cell used in this calculation
included both the water initially added to the flotation cell as well as the distilled water which was
added to maintain the pulp level. This added water was dosed with frother at the same concentration
as that added at the beginning of the test (i.e., 20 mg/L) with the aim of achieving a relatively constant
concentration of frother in the cell throughout each experiment. The equation to calculate water
recovery is shown as follows:
w1
Rw = (1)
w2 + w3
where w1 is the weight of water in the foam concentrate, w2 is the water initially added to the flotation
cell, and w3 is distilled water which was added to maintain the pulp level. Caution should be
required when comparing the water recovery values presented in this paper with those presented
elsewhere, as they may have been calculated differently. The recovery by entrainment was virtually
the water-recovered value corrected by the degree of entrainment. The simplified model of gangue
recovery by entrainment commonly seen in the literature is as follows [21]:

Rent,i = ENTi ·Rw (2)

where Rent,i is the recovery by entrainment (for particle size i), Rw is the water recovery, and ENTi is
the degree of entrainment for particle size i. An empirical mathematical model [16] for the degree of
entrainment was proposed to relate the degree of entrainment to particle size and density, as shown in
Equation (3):
1
ENTi = h i0.689 (3)
1 + 0.061· (ρs − ρw )·di 2
where ρs is the specific gravity of the solid particles, ρw is the density of the water, di is the particle
diameter. It should be noted that in the experiments performed in the current study only particle
size was varied, while the other operating conditions were kept constant, such as fluid viscosity and
particle shape. In addition, the parameters used by the authors are not the same as those used by
Wang et al. [22].

2.2.3. Laser Particle Size Experiments

For the particle size analysis, 2.0 g of single mineral was taken and made up to 40 mL after the
addition of distilled water in 1000-mL beakers. The corresponding flotation agents, which were the
same types as those used in the flotation test, were added into the pulp and stirred for 5 min. The mean
size of the pulp was then measured with a laser particle size analyzer at a spindle speed of 1900 rpm
(MasterSizer 2000, Malvern Panalytical Ltd., Malvern, UK).
 Minerals2019,
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2.2.4. Image Analysis

2.2.4. Image Analysis
An optical microscope equipped with a digital camera was used to observe the fine particle
An optical microscope equipped with a digital camera was used to observe the fine particle
flocculation. The sample was prepared by dropping it on a glass plate, followed by putting a thin
flocculation. The sample was prepared by dropping it on a glass plate, followed by putting a thin glass
glass slide on the sample to fix it. During the observation, the floc particles were photographed [15].
slide on the sample to fix it. During the observation, the floc particles were photographed [15].
2.2.5.
2.2.5.Batch
BatchFlotation
Flotation
The
Thebatch
batchflotation
flotationtests were
tests werecarried outout
carried in the XFD
in the flotation
XFD cell cell
flotation withwith
a volume capacity
a volume of 1 L.of
capacity
It1 is worth to notice that the three different flotation stages (roughing/scavenging/concentrating)
L. It is worth to notice that the three different flotation stages (roughing/scavenging/concentrating)
conducted
conductedininthe thedifferent
differentflotation
flotationmachines,
machines,but butthetheequipment
equipmentmodel modelisisthethesame
samewithwiththe
thesame
same
size of the cell. The feed samples with particle size −25 µm/+25 µm were used in tests.
size of the cell. The feed samples with particle size −25 µm/+25 µm were used in tests. The flotation The flotation
concentration (55%, mass
concentration (55%, masspercent)
percent) was
was adjusted
adjusted to a to a desired
desired level bylevel by tapThe
tap water. water. The flowsheets
flotation flotation
flowsheets of the experiments were shown
of the experiments were shown in Figure 2a,b. in Figure 2a,b.

(a) (b)

(c)

Figure 2. The batch flotation flowsheets of the (a) +25 µm; (b) −25 µm and (c) −74 µm ore (c) (the unit
Figure 2. The batch flotation flowsheets of the (a) +25 µm; (b) −25 µm and (c) −74 µm ore (c) (the unit
of dosage is g/t).
of dosage is g/t).
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Besides, the flotation flowsheet of the normal experiment (without staged-flotation) was shown
in FigureBesides, the
2c. Allthe flotation
of flotation
the flowsheet
concentrate and of the normal experiment (without staged-flotation)
thewas shown
Besides, flowsheet of tailings were
the normal filtered, dried
experiment and staged-flotation)
(without weighed. All of was closed-
shown in
in Figure
circuit 2c.
experimentsAll of the
were concentrate
repeatedand and tailings
fivetailings
times, and were filtered, dried and weighed. All of the closed-
Figure 2c. All of the concentrate werethe resultsdried
filtered, wereand
averaged respectively
weighed. All of theat the end.
closed-circuit
circuit experiments were repeated five times, and the results were averaged respectively at the end.
experiments were repeated five times, and the results were averaged respectively at the end.
3. Results and Discussion
3. Results and Discussion
3. Results and Discussion
3.1. Flotation Results
3.1. Flotation
3.1. Flotation Results
Results
3.1.1. Analysis of the Difference in Flotation Behavior
3.1.1. Analysis of the
3.1.1. the Difference
Difference in in Flotation
Flotation Behavior
Behavior
Figure 3 shows the relationship between the collector dosage and the flotation recovery of
malachite Figure
and 33azurite.
Figure showsItthe
shows the
was relationship
relationship between
between
indicated that the collector
the
the collectorcollector
ISX hasdosage
dosage and
strongand the flotation
the
collectionflotation recovery
recovery
performance of
for of
malachite
malachite and
and azurite.
azurite. It was indicated
indicated that the
the collector
collector ISX
ISX has
has strong
strong collection
collection
the azurite, the flotation recovery exceeded 95% when the dosage of ISX was 150 mg/L. However, the performance
performance for
for
the azurite,
the
recovery the
the flotation
flotation
of malachite recovery
recoveryexceeded
was relatively exceeded
lower 95%
only95% when
near 80%the
when dosage
the
under the of
dosage ISXISX
of
same waswas150150
conditions. mg/L. However,
mg/L. the
However,
recovery
the recoveryof malachite
of malachitewaswasrelatively lower
relatively only
lower near
only 80%80%
near under thethe
under same conditions.
same conditions.

Figure
Figure 3. The
3. The recovery
recovery of copper
of copper oxide
oxide oreore under
under conditions
conditions of of different
different collector
collector dosage
dosage (pH
(pH = 8.5).
= 8.5).
Figure 3. The recovery of copper oxide ore under conditions of different collector dosage (pH = 8.5).
After
After careful
careful analysis,
analysis, it was
it was found
found that
that thethe cause
cause of of
thethe significant
significant difference
difference in in floatability
floatability
After
between
between thethecareful
twotwo analysis,
minerals
minerals may it
may was
bebe found
thethe that the
distribution
distribution cause
of of grain
grain of the
size,
size, asassignificant
shown
shown inin difference
Figure
Figure 4. 4. in floatability
between the two minerals may be the distribution of grain size, as shown in Figure 4.

Figure
Figure 4. Particle
4. Particle sizesize analysis
analysis results
results of azurite
of azurite andand malachite.
malachite.
Figure 4. Particle size analysis results of azurite and malachite.
Obviously,
Obviously, thethe particle
particle size
size distribution
distribution of of malachite
malachite in in
thethe−10−10
µmµm was
was much
much higher
higher than
than that
that
of of
thetheObviously,
azurite,
azurite, whichtheisparticle
which is
one one size
of of
thethedistribution
most
most likely
likely ofreasons
malachite
reasons why
why inthe
the the −10 µm
flotation
flotation was much
recovery
recovery higher
of of than
malachite
malachite was that
was
of
lowerthe azurite,
than that which
of the is one
azurite. of the most
Therefore, likely
we focusreasons
on thewhy the
specific flotation
particle recovery
size −10 µm
lower than that of the azurite. Therefore, we focus on the specific particle size −10 µm in order to find of malachite
in order to was
find
lower than that of the azurite. Therefore, we focus on the specific particle size −10 µm in order to find
Minerals 2019, 9, x FOR PEER REVIEW 7 of 13
Minerals 2019, 9, 595 7 of 13
a suitable method to further improve the flotation recovery of malachite. Details are shown in the
next section.
a suitable method to further improve the flotation recovery of malachite. Details are shown in the
next
3.1.2.section.
The Collecting Performance of the New Collector ZH-1

3.1.2.Figure 5 showsPerformance
The Collecting the relationship
of thebetween the collector
New Collector ZH-1 dosage and the recovery of −10 µm
malachite. It was demonstrated that the recovery of malachite increases significantly as the amount
Figure 5 shows the relationship between the collector dosage and the recovery of −10 µm malachite.
of collector increases, until the dosage exceeds 150 mg/L and 250 mg/L for ISX and ZH-1, respectively.
It was demonstrated that the recovery of malachite increases significantly as the amount of collector
It was clear that the use of ISX alone has lost its effectiveness in flotation of fine-grained malachite.
increases, until the dosage exceeds 150 mg/L and 250 mg/L for ISX and ZH-1, respectively. It was clear
But the new type of xanthate (ZH-1, C3-5 carbon chain xanthate combination) shown a high-efficiency
that the use of ISX alone has lost its effectiveness in flotation of fine-grained malachite. But the new
collection performance for fine-grained malachite. Especially, the recovery of fine-grained (−10 µm)
type of xanthate (ZH-1, C3-5 carbon chain xanthate combination) shown a high-efficiency collection
malachite even more than 95% when the ZH-1 dosage was 150 mg/L.
performance for fine-grained malachite. Especially, the recovery of fine-grained (−10 µm) malachite
However, it should be noted that the ZH-1 contains a small amount of alcohols because of the
even more than 95% when the ZH-1 dosage was 150 mg/L.
production process and purity of the product, which means it possessed a certain foaming ability
However, it should be noted that the ZH-1 contains a small amount of alcohols because of the
[23]. The single mineral experiment, recovery rising sharply for fine-grained malachite was possibly
production process and purity of the product, which means it possessed a certain foaming ability [23].
more attribute to rich bubble inclusions rather than the collecting property as a collector. Therefore,
The single mineral experiment, recovery rising sharply for fine-grained malachite was possibly
subsequent chapters will explore this conjecture to determine whether the new collector ZH-1 is truly
more attribute to rich bubble inclusions rather than the collecting property as a collector. Therefore,
effective with the recovery of fine-grained malachite, or simply because of the ability like foaming
subsequent chapters will explore this conjecture to determine whether the new collector ZH-1 is truly
agent.
effective with the recovery of fine-grained malachite, or simply because of the ability like foaming agent.

Figure 5. Relationship between the collector dosage and the recovery of fine-grained malachite
Figure
(pH 5. Relationship between the collector dosage and the recovery of fine-grained malachite (pH =
= 8.5).
8.5).
3.2. Flotation Entrainment Rate Analysis
3.2. Flotation Entrainment
The collective Rate
effect of theAnalysis
new collector ZH-1 can be verified through the experimental results
of theThe actual recovery
collective and
effect of the
the entrainment
new collectorrecovery.
ZH-1 canThe ASEP (150
be verified mg/L)
through was
the used as activator,
experimental results
sodium sulfide (200 mg/L) as vulcanizing agent, pulp pH = 8.5 and MIBC
of the actual recovery and the entrainment recovery. The ASEP (150 mg/L) was used as activator, (20 mg/L) as frother at pulp
pH = 8.5sulfide
sodium in this (200
experiment.
mg/L) as vulcanizing agent, pulp pH = 8.5 and MIBC (20 mg/L) as frother at pulp
pH =In 8.5the
in experimental
this experiment. test system, the average particle size of the particles was less than 30 µm,
so it can be assumed that
In the experimental test all the malachite
system, particles
the average were size
particle closeoftothe
being spherical
particles was particles;
less than 30secondly,
µm, so
the viscosity
it can be assumedof the that
slurry
allwith different collector
the malachite particlesgrades of malachite
were close to beingunder the condition
spherical particles; of adding the
secondly,
collector
viscosityusing of therheometer
slurry with test, the results
different show that
collector gradestheof
viscosity
malachiteof the pulpthe
under tends to be the
condition ofsame
addingunder
the
the three-grain
collector using condition,
rheometerwhichtest, theis about 1 mPa·s,
results which
show that theisviscosity
the viscosity of water
of the at room
pulp tends to temperature
be the same
(20 ◦ C). This is because the concentration of the slurry used in the single mineral flotation test is as
under the three-grain condition, which is about 1 mPa·s, which is the viscosity of water at room
low as
temperatureabout(20 4.7%,
°C).resulting in the the
This is because viscosity of the slurry
concentration of thebeing
slurryclose
used to
in the single
viscosity of water
mineral [16].
flotation
In
testsummary,
is as low this experiment
as about can be calculated
4.7%, resulting by theofempirical
in the viscosity the slurry formula provided
being close to theinviscosity
Section of2.2.2.
water
[16]. Table 3 and Figure
In summary, this 6experiment
show the results
can beofcalculated
the actual by
collection ability of
the empirical different
formula collectors
provided infor each
Section
size
2.2.2.fraction of malachite. It can be seen from the results that the two collectors have obvious effects
on the capture of two fractions of −38 + 25 µm and −25 + 10 µm malachite, and the actual recovery
Minerals 2019, 9, x FOR PEER REVIEW 8 of 13
Minerals 2019, 9, 595 8 of 13
Table 3 and Figure 6 show the results of the actual collection ability of different collectors for
each size fraction of malachite. It can be seen from the results that the two collectors have obvious
(RAct : Total
effects recovery
on the captureminus
of twothefractions
entrainment recovery
of −38 + 25 µm Rent.i ) was
and −25increased
+ 10 µm to over 90%.and
malachite, Although the
the actual
collection performance for both of collector ZH-1 and ISX is similar, the entrainment
recovery (RAct: Total recovery minus the entrainment recovery Rent.i) was increased to over 90%. recovery of the
three size fraction
Although by ZH-1
the collection was much higher
performance for boththan SIX. For improving
of collector ZH-1 and the ISX quality of concentrate
is similar, in the
the entrainment
practice production,
recovery of the three the
sizecollector
fraction bySIXZH-1
shouldwasbemuch
considered
higherpriority
than SIX. +25
forFor µm malachite
improving flotation
the quality of
during the staged flotation process. On the other hand, ISX has a poor performance
concentrate in the practice production, the collector SIX should be considered priority for +25 µm on the collection of
−10 µm malachite
malachite flotationand the actual
during the recovery
staged only increased
flotation fromOn
process. 5% to 15%.
the On the
other contrary,
hand, the collector
ISX has a poor
ZH-1 exerts aon
performance strong collectiveof
the collection effect
−10 onµm−10 µm malachite,
malachite and the andactual therecovery
actual recovery was increased
only increased from 5% to
about
to 15%.50%.
On the contrary, the collector ZH-1 exerts a strong collective effect on −10 µm malachite, and
As can
the actual be seenwas
recovery from the comprehensive
increased to about 50%.analysis, the best collector select should be considered
according to the particle size of malachite during
As can be seen from the comprehensive analysis, the staged flotation
the best process.
collector selectThis means
should the ZH-1 is
be considered
beneficial to
according to the
therecovery of malachite
particle size at −25
of malachite µm, but
during theISX shows
staged a betterprocess.
flotation collecting ability
This for malachite
means the ZH-1
+25 µm. to the recovery of malachite at −25 µm, but ISX shows a better collecting ability for
at beneficial
is
malachite at +25 µm.
Table 3. The entrainment recovery of the three size fractions in the presence and absence of collector.
Table 3. The entrainment recovery of the three size fractions in the presence and absence of collector.
Total Average Size
Collector Fraction D Rw (%) Rent.i (%) RAct (%)
Recovery% di (µm) Size
Average
Collector Fraction D Total Recovery% Rw(%) Rent.i(%) RAct(%)
−10 µm 31.11 di (µm)
4.837 63.124 25.957 5.153
Without −10−25µm + 10 µm 46.89
31.11 18.761
4.837 32.232
63.124 3.226
25.957 43.6645.153
Without −25 + −38 + 25 µm
10 µm 56.23
46.89 30.987
18.761 14.518
32.232 0.3253.226 55.90543.664
−38 + 25 −10
µm µm 56.23
49.96 30.987
4.921 14.518
72.234 34.5350.325 15.42555.905
With ISX −10 µm
−25 + 10 µm 49.96
94.89 4.921
18.887 72.234
40.124 34.535
4.061 90.82915.425
With ISX −25 + −38 + 25 µm
10 µm 96.78
94.89 30.791
18.887 15.232
40.124 0.6324.061 96.14890.829
−38 + 25 −10
µm µm 96.78
90.12 30.791
4.881 15.232 40.939
75.983 0.632 49.18196.148
−10 µm
With ZH-1 −25 + 10 µm 90.12
98.72 4.881
18.564 75.983
51.231 40.939
9.201 89.51949.181
With ZH-1 −25 + −38 + 25 µm
10 µm 98.72
99.81 18.564
30.654 51.231
45.324 4.699.201 95.12089.519
−38 + 25 µm 99.81 30.654 45.324 4.69 95.120

Figure 6. The recovery of true flotation via bubble attachment of the three size fractions in the presence
Figure 6. The recovery of true flotation via bubble attachment of the three size fractions in the presence
and absence of collector (200 mg/L, pH = 8.5; the red marked represented the best true flotation recovery
and absence of collector (200 mg/L, pH = 8.5; the red marked represented the best true flotation
for the three fractions of malachite).
recovery for the three fractions of malachite).
3.3. Laser Particle Size Analysis
3.3. Laser Particle Size Analysis
Figure 7 shows the relationship between different collectors and the average particle size of
Figure It7 was
malachite. shows the relationship
indicated between
that the average different
particle sizecollectors
of −10 µm and the average
malachite particle
was about sizeµm.
4.641 of
malachite. It was indicated that the average particle size of −10 µm malachite was about
When the ISX and the IPX were added, the average particle size of the malachite was essentially 4.641 µm.
When the ISX
unchanged. Onand
thethe IPXhand,
other weretheadded, the average
malachite particleparticle size of sharply
size increased the malachite was
to 9.631 µmessentially
when the
Minerals 2019, 9, x FOR PEER REVIEW 9 of 13
Minerals 2019,
Minerals 2019, 9,
9, 595
x FOR PEER REVIEW 99 of 13
of 13
unchanged. On the other hand, the malachite particle size increased sharply to 9.631 µm when the
unchanged. On the other hand, the malachite particle size increased sharply to 9.631 µm when the
ZH-1as collector was used. ZH-1 has a strong flocculation ability, and the fine-grained malachite can
ZH-1as
ZH-1as collector
collector was
was used. ZH-1 has
used. ZH-1 has aa strong
strong flocculation
flocculation ability,
ability, and
and the
the fine-grained
fine-grained malachite
malachite can
can
be flocculated into a mass then increase the probability of collision with bubbles, thereby improving
be
be flocculated into a mass then increase the probability of collision with bubbles, thereby improving
flocculated into a mass then increase the probability of collision with bubbles, thereby improving
the recovery of the fine-grained malachite [17,24].
the
the recovery
recovery of
of the
the fine-grained
fine-grained malachite
malachite [17,24].
[17,24].

Figure 7.
Figure 7. The
The effect of different
effect of different collectors
collectors on
on the
the average
average particle
particle size
size of
of malachite
malachite(−10
(−10 µm).
µm).
Figure 7. The effect of different collectors on the average particle size of malachite (−10 µm).
3.4. Microscopic Analysis
3.4. Microscopic Analysis
The flocculation
flocculation ofof the fine-grained
fine-grained mineral
mineral particles
particles after
after the
the addition
addition of of the ZH-1 collector was
The
analyzed flocculation of the fine-grained mineral particles after the addition of the ZH-1 collectorofwas
analyzed by by electron
electronmicroscopy,
microscopy,and andthe results
the areare
results shown
shown in Figure
in Figure 8. According
8. Accordingto the image
to the image the
of
analyzed
fine by electron microscopy, and the results are shown in Figure 8. According to the image of
the particles, these these
fine particles, appearappear
dispersed throughout
dispersed the fieldthe
throughout of view,
field but the fine
of view, butparticles
the fine condensed
particles
the
into fine particles,
a massinto
when these appear
the collector dispersed throughout the field of view, but the fine particles
condensed a mass when theZH-1 was ZH-1
collector added.was Inadded.
addition, Figure 8 also
In addition, demonstrates
Figure that the
8 also demonstrates
condensed into
fine-grained a mass
minerals when
also theadsorbed
can be collector ZH-1 was added. Inlarger
addition, Figure 8 also demonstrates
that the fine-grained minerals also can be on the surface
adsorbed of the
on the surface ofgranular
the largerminerals,
granularit is beneficial
minerals, it
that
to the fine-grained
increase the mineral minerals
particle also
size can
and be adsorbed
promote the on the surface
adsorption of of the larger
mineral granular
particles on the minerals,
surface it
of
is beneficial to increase the mineral particle size and promote the adsorption of mineral particles on
is beneficial
the bubble to increase the mineral particle size and promote the9. adsorption of mineral particles on
surfacetoofachieve bubble
the bubble mineralization,
to achieve as shown
bubble mineralization, in Figure
as shown in Figure 9.
the surface of the bubble to achieve bubble mineralization, as shown in Figure 9.

Particles are scattered

Particles are scattered

Fine flocculation
Fine flocculation

Figure 8. Distribution of malachite particles under the microscope before and after adding ZH-1.
Figure 8. Distribution of malachite particles under the microscope before and after adding ZH-1.
Figure 8. Distribution of malachite particles under the microscope before and after adding ZH-1.
Minerals 2019, 9, 595 10 of 13
Minerals 2019, 9, x FOR PEER REVIEW 10 of 13

Mineralized bubble

Fine flocculation

Figure 9.
Figure Analysis of
9. Analysis of mineralized
mineralized bubble
bubble by
by microscope
microscope imagine.
imagine.
3.5. Locked-Cycle Tests of Grading Flotation
3.5. Locked-Cycle Tests of Grading Flotation
The technical approach used in the Dishui Copper Processing Plant in the past was ungraded
The technical approach used in the Dishui Copper Processing Plant in the past was ungraded
direct flotation (two roughing, three concentrating, three scavenging steps). The reagent regime was:
direct flotation (two roughing, three concentrating, three scavenging steps). The reagent regime was:
grinding fineness −0.074 mm 93.98%, the dosage of ASEP and sodium sulfide were 800 g/t respectively,
grinding fineness −0.074 mm 93.98%, the dosage of ASEP and sodium sulfide were 800 g/t
and the addition of collector ISX was 1200 g/t, the water glass was used as dispersing agent in rough
respectively, and the addition of collector ISX was 1200 g/t, the water glass was used as dispersing
selections with 1000 g/t, the perfect pulp pH value in the flotation was about 8.5–9.0. The indicators
agent in rough selections with 1000 g/t, the perfect pulp pH value in the flotation was about 8.5–9.0.
obtained by the open circuit experiment were indicated in Table 6.
The indicators obtained by the open circuit experiment were indicated in Table 6.
3.5.1. Locked-Cycle Test of +25 µm
3.5.1. Locked-Cycle Test of +25 µm
500 g of dry ore was taken each time, then 50% grinding concentration were ground for 3 min
500mm
(−0.074 g ofcontent
dry ore91.18%,
was taken eachmm
−0.025 time, then 50%
content grinding
64.19%). concentration
Grinding productswere
wereground
sieved byfor 25
3 min
µm
(−0.074 mm content 91.18%, −0.025 mm content 64.19%). Grinding products were sieved
quasi-screens. The on-screen products were selected and remove to a 1.0L flotation cell for flotation by 25 µm
quasi-screens.
operation. The The on-screenexperiment
locked-cycle products were
flow selected and in
sheet shown remove
Figureto2a,
a 1.0L flotation
and the cell for
test results flotation
were listed
operation. The locked-cycle experiment flow sheet shown in Figure 2a, and the test results were
in Table 4. It can be seen from the results that the collector ISX shown a good selective collection ability listed
in
on Table
+25 µm4. copper
It can be seenore,
oxide from the
and results
the copper that the in
grade collector ISX shown
the tailings a good
was only 0.14%,selective
and thecollection
recovery
ability on +25 µm copper oxide ore,
was up to 91.94% with a grade of 18.24%. and the copper grade in the tailings was only 0.14%, and the
recovery was up to 91.94% with a grade of 18.24%.
Table 4. Flotation grade and recovery of +25 µm malachite.
Table 4. Flotation grade and recovery of +25 µm malachite.
Grading Flotation Product Yields /% Cu Recovery /% Cu Grade /%
Grading Flotation Product Yields /% Cu Recovery /% Cu Grade /%
Concentrate 8.05 91.94 18.24
Concentrate 8.05 91.94 18.24
+25 µm Tailing 91.95 8.06 0.14
+25 µm Tailing 91.95 8.06 0.14
+25 µm 100 100 1.6
+25 µm 100 100 1.6

3.5.2. Locked-Cycle
3.5.2. Locked-Cycle Test of −25
Test of µm
−25 µm
After sedimentation
After sedimentation of of the
the product
product under
under the
the sieve
sieve (−25 was clarified,
µm) was
(−25 µm) clarified, the
the supernatant
supernatant liquid
liquid
was
was poured
pouredout outasasthe
theflotation
flotationwater,
water,and thethe
and 1.51.5
L flotation cell cell
L flotation is used for flotation.
is used The locked-cycle
for flotation. The locked-
experiment flow sheet shown in Figure 2b, and the test results were listed in
cycle experiment flow sheet shown in Figure 2b, and the test results were listed in Table Table 5. It can be5.seen
It canfrom
be
the results
seen from that the collector
the results that theZH-1 shownZH-1
collector a good selective
shown collection
a good selective ability for −25ability
collection µm copper
for −25 oxide
µm
ore, andoxide
copper the copper grade
ore, and in copper
the the tailings was
grade inonly
the 0.24%,
tailingswhich
was onlyrealizes efficient
0.24%, flotation
which recovery
realizes of
efficient
fine-grained copper oxide.
flotation recovery of fine-grained copper oxide.

Table 5. Flotation grade and recovery of −25 µm malachite.

Grading Flotation Product Yields /% Cu Recovery /% Cu Grade /%

Concentrate 3.96 75.60 18.03
−25 µm Tailing 96.04 24.40 0.24
−25 µm 100.00 100 0.94
Minerals 2019, 9, 595 11 of 13

Table 5. Flotation grade and recovery of −25 µm malachite.

Grading Flotation Product Yields /% Cu Recovery /% Cu Grade /%

Concentrate 3.96 75.60 18.03
−25 µm Tailing 96.04 24.40 0.24
−25 µm 100.00 100 0.94

Table 6 shows the flotation grade and recovery of malachite with or without staged flotation
operation. The results indicated that the copper oxide flotation recovery increased from 79.67% to
83.38%, and the grade also raised from 18.08% to 18.14% after using the staged flotation technology.
The staged flotation process was quite effective for the recovery of copper oxide at the Dishui Copper
Processing Plant. However, it was necessary to consider the economic feasibility since the use of staged
flotation requires the transformation of existing equipment and plants.

Table 6. Flotation grade and recovery of malachite with or without grading flotation operation.

Category Product Yields /% Cu Recovery /% Cu Grade /%

Concentrate 5.39 83.38 18.14
With Grading Flotation Tailing 94.61 16.62 0.21
Raw ore 100 100 1.17
Concentrate 5.14 79.67 18.08
Without Grading Flotation Tailing 94.86 20.33 0.25
Raw ore 100 100 1.17

3.6. Economic Feasibility Analysis

(1) Analysis of new economic benefits
After expansion of the Dishui Copper Processing Plant, the annual ore dressing capacity will
reach 1 million tons, and the copper grade of raw ore was about 1.0%. The annual increase in metal
copper output will increase by one recovery rate:

1,000,000 ton × 1.0% × 1% = 100 ton (4)

According to the current market copper price of 6571 US $/ton, the return rate of 82%, each increase
in the recovery rate will increase the metal copper sales revenue:

100 ton × 6571 US $/ton × 82% = 657,100 US $ (5)

The closed-circuit test results show that the staged flotation process can increase the copper
recovery by more than 3%. Increasing the recovery by 3% will increase the output of metal copper by
about 300 ton per year, increase the sales revenue by about 1.9 million US$, and after deducting 17% of
the value-added tax, increase the gross profit by about 1.6 million US$.
(2) Investment and cost increase analysis
To use the mud-sand sorting process, an additional set of cyclones and a flotation system are
required. The flotation system can use the original 1000T mineral processing plant idle flotation
equipment (the power of a single unit is 7.5 KW, a total of 18 flotation machines), the swirling device
grading effect will have a greater impact on the yield of +25 µm, so it is necessary to select according to
the fine characteristics of the grinding products and the requirements of fine-grain grading. The addition
of a flotation system will result in an additional three flotation operators (salary about 8000 US$ for
one person per year), and some input will be required for water and electricity consumption and
spare parts.
Minerals 2019, 9, 595 12 of 13

4. Conclusions
The collector ISX has strong collection performance for azurite, and the flotation recovery exceeded
95% when the dosage of ISX was 150 mg/L. However, under the same conditions, the recovery of
malachite was relatively low, only near 80%, due to the higher particle size distribution in the −10 µm
than that of the azurite. Use of ISX alone has lost its effectiveness in flotation of fine-grained malachite,
but a new type of xanthate (ZH-1, a C3-5 carbon chain xanthate combination) has shown a high-efficiency
collection performance for fine-grained malachite. Especially, the recovery of −10 µm malachite was
higher than 95% when the ZH-1 dosage was 150 mg/L.
The two collectors (ISX and IPX) had obvious effects on the capture of two fractions of −38 + 25 µm
and −25 + 10 µm malachite, and the actual recovery was basically increased to over 90%. The collector
ZH-1 showed a strong collection ability for −10 µm malachite, and the actual recovery was increased
to about 50%, due to its strong flocculation ability, with the average particle size of −10 µm malachite
sharply increasing from 4.641 µm to 9.631 µm.
The copper oxide flotation recovery increased from 79.67% to 83.38%, and the grade also raised
from 18.08% to 18.14% after using the staged flotation technology. This technology was quite effective
for the recovery of copper oxide at the Dishui Copper Processing Plant, successfully increasing the
gross profit by about 1.6 million US$ per year.

Author Contributions: R.Z., G.G., Z.C. conceived and designed the experiments; R.Z. and S.S. performed the
experiments and analyzed the data; R.Z. and G.G. contributed reagents and materials; R.Z., Z.C. and Y.W. wrote
the paper.
Funding: The authors acknowledge the support of the National Natural Science Foundation of China
(No. 51374249), the National Key Technology R&D Program (No. 2015BAB12B02) and the Science and Technology
Planning Project Guangdong Province, China (No. 2013B090800016).
Conflicts of Interest: The authors declare no conflict of interest.

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