Journal of Cleaner Production 279 (2021) 123705

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review

Ore agglomeration behavior and its key controlling factors in heap

leaching of low-grade copper minerals
Leiming Wang a, b, Shenghua Yin a, b, *, Aixiang Wu b
a
Key Laboratory of the Ministry of Education of China for High-Efficient Mining and Safety of Metal Mines, University of Science and Technology Beijing,
Beijing, 100083, China
b
School of Civil and Resources Engineering, University of Science and Technology Beijing, Beijing, 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: The particle segregation, stratification, excessive feed size of non-agglomerated heaps chronically leads
Received 28 November 2019 to poor heap permeability and leaching efficiency. Thus, owing to well-developed dual pore structure,
Received in revised form desirable liquid retention and better leachability, the ore agglomeration has been widely utilized to
28 July 2020
recover copper metals from copper sulfides and oxides. To better understand the effect of agglomerations
Accepted 9 August 2020
Available online 23 August 2020
behavior on leaching reactions and promote its operating condition, the typical findings of industrial
cases, controlling factors and leaching mechanisms are critically reviewed in this study. Specifically, this
Handling Editor: Prof. Jiri Jaromir Kleme
s paper basically discusses three pivotal questions tightly related to the industrial requirements: 1) the
process of efficiently obtaining the well-shaped, leachable ore agglomerations via key factors and pa-
Keywords: rameters; 2) the evaluation of the single agglomeration or agglomerated heaps via quality evaluation and
Ore agglomeration procedure controlling; 3) the effect of ore agglomeration on enhanced leaching behavior via mass
Heap leaching transfer, dual pore structure and flow behavior. Relied on these typical research progress and break-
Copper sulfide throughs, this paper proposed prospect opinions and potential studies that offer a good reference to
Copper oxide
operation of industrial agglomerated heaps.
Enhanced leaching
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Application of industrial agglomeration heaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Key parameters and process controlling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Agglomeration preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.1. Mineralogy and chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.2. Particle size distribution (PSD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.3. Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.4. Device and its setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.5. Curing and additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2. Quality evaluation of agglomeration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.1. Direct inspection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.2. Wet/dry strength and stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.3. Leachability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.3. Mass transfer and enhanced leaching mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3.1. Mass transfer enhancement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3.2. Bio/chemical compaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3.3. Pre-treatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.4. Dual-pore structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

* Corresponding author. Key Laboratory of the Ministry of Education of China for High-Efficient Mining and Safety of Metal Mines, University of Science and Technology
Beijing, Beijing, 100083, China.
E-mail addresses: ustb_ysh@163.com, csuysh@126.com (S. Yin).

https://doi.org/10.1016/j.jclepro.2020.123705
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705

3.4.1. Intra-/inter-particle porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

3.4.2. Minerals inlay and dual-pore porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.4.3. Leaching and dual-pores evolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.5. Flow behavior and percolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.5.1. Flow paths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.5.2. Liquid retention and hysteresis behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.5.3. Heap permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.6. Commercial issues and controls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4. Conclusion and prospect outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

1. Introduction pollution (Jerez, 2017; Li et al., 2014). It resulted in serious envi-

ronmental pollution and casualties in mines, which did not meet
Copper minerals are the fundamental natural resources that the requirements of cleaner production and sustainable develop-
heavily supported the economic development, which are one of the ment, and required transformation and exploration of suitable
important chips in industrial constructions. According to Henckens copper mining methods (Calvo et al., 2016). As an efficient,
et al. (2019), more than 80% of industrial raw materials and 70% of environmental-friendly and low-cost mining method, the solution
agricultural materials were relied on the mining engineering, mining has been widely utilized in the United States, Canada, China,
especially for copper minerals developments. Thus, the exploration Chile, South Africa and India, therefore, plenty of industrial copper
of strategic metal minerals like chalcopyrite, pyrite and chalcocite is recovery cases are successfully built to process low-grade minerals,
essential issue, which is tightly related to electricity, construction, waste printed circuit boards (PCBs) and tailings (Ilankoon et al.,
military, aerospace and communication around the world (Johnson, 2018). Judging by the differences of ore particle size distribution
2014; Petersen, 2016). (PSD), agglomeration, crushing, irrigation and operation parame-
However, the average grade of copper minerals gradually ters (John, 2011), the solution mining could be basically divided into
decreased after long, excessive mining period. For instance, the in-situ leaching (ISL), dump leaching (DL), heap leaching (HL), vat
data from Intelligence Mine showed that the average grade of leaching (VL) and agglomerated heap leaching (AHL). Table 1 pro-
copper minerals become obviously lower and lower in Bingham posed the key parameters and its common controlling factors in the
Canyon Mine of the United States (Fig. 1). Moreover, unlike energy industrial applications.
minerals (e.g. coal, oil), the copper mineral resources are less In 1970s, to ameliorate the undesirable leaching condition and
endowed that secondary minerals occupy a dominant percentage, obtain better extraction efficiency, the agglomeration and its pro-
which the average copper grade is less than 0.87% in China (Yin cessing controls were firstly mentioned in Nevada of the United
et al., 2018b). Due to the consideration of high-period infrastruc- States (Johnson and Roberto, 1997; Potter, 1981). As Fig. 2 shows,
ture and high crushing costs, it is not an ideal method to recycle the basic operating procedure of agglomerated heap could be
from low-grade copper minerals using the conventional under- described that: 1) the coarse ores were crushed into fine or small
ground or surface mining methods (Chen et al., 2016). particles in the crushers; 2) the chemical binders (e.g. sulfuric acid
Moreover, the traditional and extensive mining process has solution) were mixed with crushed ores, and obtained agglomer-
caused many environmental problems, such as: surface subsidence, ations in the drummer; 3) agglomeration curing period; 4) stacking
underground rock burst, farmland damage, and groundwater and leaching process. Differentiated by the agglomeration device,
the ore agglomeration is commonly divided into the drum
agglomeration (accounted for 69%) and conveyor agglomeration
(31%). The liquid retention of agglomerated heap is much desirable
due to its well-developed intra-particle pores, which obviously
improve the mass transfer and accelerate leaching reaction. Based
on the industrial data, the permeability in the agglomerated heaps
could improve by 10e100 times, the leaching time could shorten by
1/3e1/2 times, the acid consumption could reduce by 20e30%, and
the Cu extraction rate could increase by 10e30%. As a result, ore
agglomeration is thought as one of key strategies in the extraction
of copper oxides, copper sulfides, laterite nickels, and uranium
minerals (Lin et al., 2005; McClelland et al., 1983).
In short, as an effective, innovate methods, ore agglomerations
directly affected the intra-particle pores and liquid retention of
heap, thus, potentially affecting the recovery of valuable metallic
minerals (Bleiwas, 2012; Schaefer and Nirschl, 2010). Similar with
the other technological processing methods, ore agglomeration has
its own suitable operation condition and distinctive advantages
(Petersen, 2017). According to Bouffard (2005), the concept of
“5Ws” (who, what, when, where, and why) was firstly proposed
Fig. 1. Evolution of copper ore mill grade at the Bingham Canyon Mine, USA.
(Fig. 3) to correspondingly describe the basic features of crushed
 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705 3

Table 1
Key parameters and features of typical solution mining.

Type Particle size/mm Crushing Agglomeration Irrigation rate//L$m
2 h
1 Heap height/m Leaching period/year Leaching extraction/%

ISL þ1000 No / / / Cu: >5 5e50

U: 1e3
DL
1000 þ 30 No No 2e15 8e75 Cu:>10 20e85
Au: 2e6
Hl
100 þ 5 Yes Majority 2e15 2e10 Cu: 1e4 40e97
Ni: 1e5
U: 1e3
Au: 0.1e2
VL
10 þ 0.5 Yes Depended 10e50 1e5 4e30 days 80e97
AHL
1þ0.25 Yes Yes 2e15 1e5 / 70e97

Fig. 2. Scheme of industrial ore heap with agglomeration process.

ore agglomerations. It mainly includes the following five aspects:
suitable feed minerals (who), definition & basic procedure (what),
optimal condition (when), agglomeration equipment and device
(where), and operation advantages (why).
The agglomerated heaps could mainly have three distinctive
advantages than non-agglomerated heaps, which were tightly
related to pore structure, fluid seepage condition and bio/chemical
reaction efficiency. The details descriptions were expressed as
follow:
1) Ameliorating the dual-pore structure (i.e. inter- and intra-
particle pore) of unsaturated agglomerated heaps. The pore
network of non-agglomerated ore heaps mainly composed of
inter-particle pores, whereas the intra-particle pores were un-
developed. The ore agglomeration composed of core and porous
shell (Fig. 4a), where fine particles attached on the surface of
coarse particles. Thus, the potential flow paths were more
develop in agglomerated heaps (Chamberlin, 1981; Nosrati et al.,
2012c). The intra-particle porosity of agglomerated heaps
obviously improved by eliminating immigration of fine pow-
ders. At the same time, the undesirable flow paths clogging,
particle segregation and particle stratification appeared in
stacking process were basically avoided (van Staden and
Petersen, 2019, 2018; Wang et al., 2020b).
2) Avoiding the premature formation of preferential flow or un-
desirable flow behavior. Driven by gravity and capillary forces,
the liquid spread randomly in industrial heaps where the un-
saturated and saturated liquid condition simultaneously co-
existed (Fagan et al., 2014; Wu et al., 2007). The well-
developed pore structure of agglomeration delayed the un-
timely formation of preferential flow paths (Fig. 4b). The over-
much immigration or even compaction of fine particle in
agglomerated heaps were hard to appear due to desirable
permeability and developed dual porosity. Thus, the liquid
diffused and disturbed more uniform in agglomeration heaps.

Fig. 3. 5Ws (who, what, when, where, and why) for crushed ore agglomeration processes.
4 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705

Fig. 4. Schematic diagram of pore structure and flow paths of agglomeration in particle-scale and bed-scale.

3) Enhancing mass transfer and bio/chemical reaction in the solid-
liquid interfaces. Under the coupled effect of electrostatic van
der Waals adsorption and chemical reaction cementation, the
adjacent fine particles adhered and formed well-developed
intra-particle pores. These intra-particle pores provided the
potential paths of liquid spreading, bacteria adsorption and
leaching reaction, which obviously increase the leaching effi-
ciency (Cross et al., 2006; Van Der Merwe et al., 2004). As a
result, the performance of liquid retention behavior in
agglomerated heap was obviously promoted that reflected by a
desirable steady liquid holdup, it accelerated the oxygen, ferric/
ferrous ions and heat diffusion (Ahmadlouydarab et al., 2011).
Besides, some additives such as acidic ferric chloride, acidic
cupric chloride, sulfuric acid solution could also be incorporated
in agglomerated preparation, which could promote the peak Cu
extraction rate (Yin et al., 2020).
2. Application of industrial agglomeration heaps
Commonly, the ore agglomeration is regarded as a pretreatment
method before stacking, which widely utilizes to promote heap
leaching operation. To better obtain the well-shaped agglomera-
tions, the additional costs including crushing, chemical binders and
agglomeration device setups should be carefully considered. In this
situation, it was more adapted to recovery precious metal resources
such as copper, gold, laterite nickel, uranium and silver minerals,
instead of iron minerals. To clearly display some industrial opera-
tions of agglomerated heaps, Fig. 5 summarized the typical indus-
trial metal heaps using ore agglomeration methods. The ore
agglomeration were widely utilized in the industrial agglomerated
heaps located in the west coasts of the United States, Canada and
Chile (Johnson, 2018). Besides, the ore agglomeration were also
utilized in the copper oxides or heaps with high-content clay, muds

Fig. 5. Typical heaps of valuable metal using ore agglomeration method.

 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705 5

and powders (Yin et al., 2018a). According to Bouffard (2008), lots
of industrial agglomerated heaps of copper minerals were suc-
cessfully built in Zaldívar Copper Mine, Collahuasi Copper Mine,
Cerro Colorado Copper Mine in Chile, and Nevada heap operation in
the United States.
To better reveal the operation condition of agglomerated heaps,
Table 2 summarized the pivotal operation parameters in agglom-
erated heaps of copper, gold and silver minerals (Bouffard, 2008;
Velarde, 2005). As Table 2 showed, the agglomerations were both
suitable for not only copper oxides but also copper sulfides. The
chemical binders used in agglomeration procedure were mainly
divided into three types: organic binders (e.g. cellulose), inorganic
binders (e.g. stucco, acid-proof) and polymer binders (e.g. poly-
acrylamide). The agglomeration of copper oxides did not need the
long-period curing, the lowest required grade of copper oxides and
sulfides were 1.45% and 1.00%, respectively. The peak Cu extraction
rate of copper sulfide and oxides were both over 70%. Due to the
complex mineralogy compositions, the leaching period of copper
sulfides was longer than 200 days.
3. Key parameters and process controlling
The ore agglomeration was one of complicated industrial
processes affected by the physical, chemical and even biological
factors simultaneously (Herna ndez-lo
 pez et al., 2011; Urtubia and
Suarez, 2020). Overall, as Fig. 6 showed, the key factors affected
agglomeration were basically divided into the following six as-
pects: 1) agglomeration preparation (e.g. mineralogy, chemical
composition, particle size distribution, chemical binders/addi-
tives, agglomerated device and its operation parameters, curing
time); 2) agglomeration quality evaluation (e.g. direct visual in-
spection, wet/dry strength, leachability, structural stability); 3)
dual-pore structure features (e.g. inter-/intra-particle porosity,
mineral inlay, pore evolution with minerals dissolution); 4) bio/
chemical bonding behavior (e.g. mass transfer, bio/chemical
compaction, pre-treatment media of sulfate chloride solution); 5)
flow behavior and percolation (e.g. flow paths, liquid retention &
spread, heap permeability); 6) commercial issues and process
controls (e.g. operation costs, environmental protection issues).
The research findings in these aforementioned aspects would be
carefully and detailed discussed in the following sections of this
paper.
3.1. Agglomeration preparation
3.1.1. Mineralogy and chemical composition
The mineralogy features include the chemical component,
mineral composition and rock hardness and so on, which tightly
affected the mining and pre-processing methods (Olubambi et al.,
2007). In the agglomeration procedure, the ore mineralogy
mainly affected chemical binders, additives, crushing size,
agglomeration drum parameters and even with/without bacterial
pre-inoculation (Nosrati et al., 2014). In this regard, Quaicoe et al.
(2014) studied the effect of feed mineralogy on the agglomeration
behavior and heap porosity by controlling the chemical composi-
tion condition (i.e. clay: kaolinite, Na-exchanged smectite; oxide:
hematite, quartz). As shown in Fig. 7a, the results indicated that
better porosity and mineralogy exposure were obtained under the
intervention of higher mass fraction sulfuric acid solution (40 wt%).
Meanwhile, Shayestehfar et al. (2008) considered the mineralogy
features of copper oxides agglomerations in Sarcheshmeh Copper
Mine, Iran. He proposed that the oxyhydroxide gradually formed
and filled the open voids around the quartz grains in acidic leaching
period (Fig. 7b).
According to Walting H.R. (2006), the copper sulfides were well
known as its complexity of mineralogy composition, which
simultaneously contained various metal minerals (e.g. chalcocite,
chalcopyrite, bornite and pyrite). Commonly, the feed raw ores
undergoes multi-step crushing and bonding to obtain well-shaped
structural agglomerations, thus, the ore agglomerations were pro-
cessed by mechanical and chemical activation duration (Mejdoub
et al., 2017), it could accelerate to liberate valuable grains
reserved in raw copper minerals. Besides, the ore agglomeration
preparation assisted by acidic chloride solution presented a po-
tential method to effectively recover copper sulfides (Wang et al.,
2020c). The acidic ferric chloride solution was uniformly sprayed
on ore particles, which promoted the agglomerated behavior and
bonding efficiency. However, the effect of feed mineralogy libera-
tion on the intra-particle porosity and mass diffusion were still not
well-known (Albijanic et al., 2011).
3.1.2. Particle size distribution (PSD)
The raw feed ores collected from surface/underground mining
process were crushed into the wide particle size distribution (PSD),
which roughly ranged from 30 mm to 0.075 mm (even finer). The
crushing devices were mainly concluded of jaw crusher, cone

Table 2
Key parameters in agglomerated heaps of copper oxides, sulfides, uranium and nickel ores.

Parameter Ore types

Copper oxides Copper sulfides Uranium Nickel ores

Ore grade/% 0.45e1.45 0.8e1.0 150e1000 ppm 0.3e2.5

Processing capillarity/Mtpa 3e56 3e21 1.4e36 0.7e3
Crushed diameter/mm 10e38 10e18 / 25e70
Heap height/m 3e10 4e11 6 4e6
Permeability evaluation good good good poor
Leaching agents H2SO4/NH3 Fe2(SO4)3/H2SO4 H2SO4/Na2CO3 H2SO4
Dosages of leaching agents/kg$t
1 8e75 6e18 15e40 >300
Irrigation rite/L$m
2$t
1 4e15 4e8 5e15 5e10
Binders type / Nalco-Extract ore 9560; cement Polymeric binder (Hi-Tex 82200TM);
Nalco anonic flocculant OPTIMIER 9960; Polyacrylamide OPTIMER AA 182H™
Stucco;
Ployacrylamide
Dosages of binders 2.5e40 1e40 15e60 5e150
Curing time / 24e240 14e336 24e168
Production costs/US$$lb
1 1.05 0.90 / /
Investment costs/US$$lb
1 30e40 35 26e75 160e350
Leaching time/d 40e180 200e600 40e100 120e250
Leaching rate/% 70e86 70e80 60e80 65e85
6 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705

Fig. 6. Key parameters and essential controlling issues of ore agglomerations heap.

Fig. 7. The mineralogy liberation and pore features of agglomeration (a) and ore morphology (b).
 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705
crusher, roll crusher, high pressure grinding rolls (HPGR) (Ergu and
Benzer, 2006; Ghorbani et al., 2013). Due to the large spans of PSD,
the proportion between fine and coarse particles was commonly
undesirable (Ghorbani et al., 2011). The PSD of feed materials
should be artificially controlled instead of randomly used in the
stacking process. However, the feed PSD of copper sulfides was
coarser, which was different from the high-clay minerals (e.g.
laterite nickels, copper oxides). The fine particles (or powders)
wrapped around coarse ores under the assistance of binders and
additives.
Overall, the PSD of feed materials directly influenced the
agglomeration diameter, dual-pore porosity, compressive strength
and potential fines immigration behavior. The PSD of feed ores
could be commonly evaluated by the uneven coefficient Cu and
curvature coefficient Cc. According to Yin et al. (2016), a higher
proportion of fine particles actually increased the structural
strength of agglomerations, whereas it potentially lead to heap
compaction with minerals dissolution attacked by acidic solution.
On the contrary, the excessive higher proportion of coarse particles
led to the poor bonding and enlargement behavior because of the
weaken contacts among coarse particles (Pepin et al., 2000;
Sebastia-Saez et al., 2018). Besides, to better quantitatively under-
stand the effect of PSD on the fine particle immigrations, adhesion,
collision and enlargement behavior, the numerical simulations (e.g.
discrete element method (DEM)) using the mathematical model
(e.g. non-linear spring-dashpot type contact models) were also
proposed. The simulation results revealed that desirable reaction
interface gradually exposed in the core enlarging process, resulting
in a higher Cu extraction rate. Besides, the PSD of feed ores affected
particle deformation and internal core formation (Liu et al., 2000;
Mishra et al., 2002).
3.1.3. Binders
Driven by the chemical and physical adsorption forces, the
adhesion/cohesion phenomenon easily appeared and observed
among adjacent coarse and fine particles in agglomerated heaps
(Degodya and Shavakuleva, 2019). Some undesirable adhesion and
cohesion forces could lead to adverse results, including fine particle
immigration, heap compaction, preferential flow and lower Cu
extraction rate, especially in non-agglomerated heaps (Wu et al.,
2009). Owing to weak connections between adjacent particles
Fig. 8. Typical physical and chemical binding mechanism assisted by chemical binders.
7
like liquid bridge, the pore structure of ore agglomeration was
unstable without the assistance of chemical binders. Therefore, to
obtain an ideal adhesion and cohesion condition, some key chem-
ical binders, such as stucco, acid-proof cements and Portland
cement were added into the agglomeration preparation of indus-
trial heaps (Yin et al., 2020).
Fig. 8 showed the coupled connection of hydraulic, chemical and
physical among adjacent ore particles under the assistance of
chemical binders. The chemical binders effectively bonded adjacent
particles by accelerating the formation of liquid bridges, liquid films
and solid bridges (Raj Kumar and Malayalamurthi, 2017). The
bonding mechanism was firstly mentioned by Rumpf H. (1990) and
Pietsch (2003, 2001) that bonding effects of binders could consist of
coupled factors, including a) solid bridge, b) adhesion and cohesion
forces, c) surface tension and capillary pressure, d) attraction forces
between solids, and e) interlocking bonds. Thus, the fine and coarse
particles was bonded under the natural bonding, physical adhesion
and chemical reaction, even biological film absorption, ultimately
obtaining agglomerations with well-developed porosity, structural
strength, and desirable leachability. In 2009, Lewandowski and
Kawatra (2009a) systematically summarized chemical binders
utilized in agglomerated heaps of copper minerals. Differentiated
from chemical features, these agglomerated binders were divided
into organic binders, inorganic binders and polymer binders.
Table 3 summarized the current industrial/laboratory binders and
its key features applied in copper agglomerated heaps.
Based on the physical/chemical features, the chemical binders
had their own merits and potential disadvantages. For instance,
Kodali et al. (2011) evaluated the effect of stucco binders on ag-
glomerations of copper oxides and sulfides in Zaldivar Copper Mine
(Fig. 9a). The results showed that the intra-particle porous pore
massively formed and surrounded the agglomerated cores under
the effect of stucco hydration reactions. The non-ionic and cationic
polyacrylamides (Lewandowski and Kawatra, 2009b; Michaels,
1954) were also used as agglomerated additives or flocculants
assisted by hydrogen bonding (Fig. 9b). The results revealed that
polyacrylamides could significantly prevent fine particles migra-
tion, whereas it was still faced with the potential negative effects on
the environmental pollution. Moreover, based on the studies of
Quaicoe et al. (2013), the effect of the initial mass fraction of sulfuric
acid solution (H2SO4) on agglomeration behavior was detected in
8 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705

Table 3
Chemical binders utilized in agglomerated heaps/experiments of copper minerals.

Type Binder Description of basic features

Organic Lignin Negligible resistance to sulfuric acid solution.

binders Cellulose Negligible resistance to acid solution.
Tall oil pitch It could improve the stability of agglomeration heap, while the long-term behavior was not desirable and still being
discussed in progress
Inorganic Sulfuric acid solution (H2SO4) It was commonly used in the mixture of copper sulfide and oxide minerals, the structural stability of agglomeration in
binders long-period leaching process was needed to be evaluated
Stucco (CaSO4$1/2H2O) It was used to obtain agglomeration using mixture minerals of copper oxides and sulfides, forming the porous layer
attached on the surface of agglomerations
Biometek-WLAG001 It was suitable to leach the mixture of copper oxides (65.79%) and sulfides. The bacteria activity was not influenced
when its concentration was over 4 g L
1
Portland cement It played binding effects by forming the crystalized ettringite under the effect of stucco hydration reactions
Polymer Acrylamide/acrylic acid It was commonly regarded as flocculant which could bond fine particles and decreased immigration, whereas
Binders copolymers/polyacrylamide detoxification and potential environmental pollution needed to be further considered
Extract-Ore 9560 It was one type of acrylamide/acrylate polymer and commonly used with cement
PloyDADMAC It was used in mixture of copper oxides and sulfides and not good at the controlling of fine particles/powders
immigrations
Polyvinyl acetate (PVAc) It was used as flocculant and had good agglomerated preference indicated by soaking, saturated leaching and long-term
unsaturated leaching
Waste treatment additive It had a desirable agglomerated behavior, which was indicated by soaking, saturated leaching and long-term
unsaturated leaching

Fig. 9. Chemical binders and its bonding mechanisms. (a) stucco, (b) polyacrylamide, (c) sulfuric acid solution (H2SO4).

the laboratory scale (Fig. 9c). It indicated that the agglomeration
diameter was tightly related to chemical composition and mass
fraction of binders. Therefore, whether the type of agglomeration
binders was, it played roles like “contacting bridge” existed in
adjacent particles to enhance the mutual absorption until these
particles attached or bonded each other (Huang et al., 2019).
Wherein, the binder type, mass fraction, operation costs and
potential environmental protects were considered as the key
operation parameters of ore agglomeration.
3.1.4. Device and its setup
The agglomeration devices and its parameter setup were deci-
sive factors affected the agglomeration quality and economic costs.
As shown in Fig. 10, differentiated from agglomerated device, the
 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705
Fig. 10. Current industrial agglomeration device and its compositions. (a) drum agglomeration, (b) conveyor/belt agglomeration; (c) disc/pan agglomeration.
industrial agglomerations divided into three types: drum agglom-
eration (Fig. 10a), conveyor/belt agglomeration (Fig. 10b), and disc/
pan agglomeration (Fig. 10c). The structure and composition of
these agglomeration devices were simplified into four key systems:
driving operation systems (i.e. electric motor), agglomerating body
system (i.e. drum, conveyor/belt, or disc/pan), additives system (e.g.
stucco and cement) and materials transporting systems (i.e. input
of feed particles and output of wetted agglomeration products). The
data showed that the drum agglomeration occupied nearly 70% of
the total industrial utilization, which regarded as was the most
commonly used device.
In term of ore agglomeration drum, the rolling speed (rpm),
rolling angle ( ), drum sizes (length/diameter, L/D) and running
period (mins) were commonly defined as important detected pa-
rameters. Nosrati et al. (2012a) developed a novel lab-scale
agglomeration drum and emphatically discussed the potential ef-
fects of process variables (e.g. drum rolling speed, running period)
on agglomeration behavior. The results showed that the size of
shaped agglomeration was sensitive to drum speed if the running
period was over 8 min. According to Miller (2009), the effect of
drum size, curing time, outflow heights, clay density and additive
position, eventually proposing the referred mathematical model to
select operation parameters of industrial agglomerated drums.
During the collisions and attachments of wetted fine particles, the
structure design including scraper, keels and additive dippers of
agglomerated drums also should be considered, which heavily
affected the diameter enlargement of ore agglomerations.
3.1.5. Curing and additives
The wetted shaped agglomerations were obtained in the output
of agglomeration drums, whereas these wetted particles were not
suitable to be directly piled in ore heaps due to a lower structural
strength of agglomerations. To further optimize this condition, the
curing period and suitable additives (e.g. deionized water) was
applied after agglomeration drum procedure (McClelland, 1986).
During the curing process, the chemical binders reacted with
ores and eventually the reaction products bonded ore particles as a
9
result. The curing period, environmental temperature, additives in
curing process should be emphatically considered in industrial
cases. For instance, the hydration reaction occurred and improve
agglomeration strength under the assistance of stucco binders. Lu
et al. (2017) investigated the minerals dissolution in the acid
curing period, the results revealed that copper oxides could be
dissolved in the acidic condition. It led to the enrichment of Cu2þ,
Fe3þ and Fe2þ in the acidic leaching media and eventually obtained
squez-ye
a desirable Cu extraction rate (Fig. 11a). Further, Vela venes
et al. (2018) focused on the copper-bearing sulfide minerals con-
sisted of chalcopyrite (89.3 wt%) and chalcocite (7.2 wt%), he found
that the longer curing period assisted by high-concentration chlo-
ride solution could shorten the leaching period and decreased the
irrigation requirements of industrial cases (Fig. 11b). Relied on
these previous studies, the desirable curing condition could be
described that: longer curing time, 20 ± 5  C environmental tem-
perature and enough additive media (6 wt% or higher). Of course,
the parameter setup of curing condition in industrial cases syn-
thetically affected by the chemical composition, feed mineralogy,
thus it should be evaluated by not only agglomeration quality but
also the industrial operation costs.
3.2. Quality evaluation of agglomeration
3.2.1. Direct inspection
To quantitatively define the bonding, leaching and also breakage
behavior of agglomeration, the quality evaluation of ore agglom-
erations could divide into direct inspection, wet/dry strength and
leachability (Luo et al., 2017). Above all, the first step was to make
sure whether the well-shaped agglomeration particles could be
obtained. The direct inspection was immediateness evaluation by
means of visual observation: 1) whether the well-shaped agglom-
eration can be efficiently obtained under the different agglomera-
tion conditions; 2) what’s the morphological characteristic of ore
agglomeration surface; and 3) how’s the bonding behavior of
adjacent shaped agglomerations. The previous studies revealed
that the agglomerated bonding was poor and hard to obtained
10 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705
Fig. 11. Chemical analysis and leaching behavior of copper minerals under controlled curing condition.
well-shaped agglomerations if the proportion of coarse particles is
higher. On the contrary, the well-shaped agglomerations were easy
to obtain when the proportion of finer feed particle was higher,
whereas the diameter of agglomerations was non-uniform (Xu
et al., 2013). The PSD of ore agglomeration could be roughly
divided into three types: uniform graded size, well graded size and
gap graded size. This compaction behavior of adjacent well-shaped
agglomerations could directly be observed via measuring the
height decrease of agglomerated heaps.
3.2.2. Wet/dry strength and stability
The structural strength and potential breakage appeared during
the agglomeration leaching could affect the inter-/intra-particle
porosity and potential flow paths formation (Blackmore, 2015),
even threated the slope stability of agglomerated heaps. According
to Garcia and Jorgensen (1997), this mechanical behavior and
structural stability of agglomerations were commonly evaluated by
the wet strength (single agglomerated particle scale) and dry
strength (agglomerated heap scale). Besides, the Shatter drop test,
and Kappes percolation test were also used in the quality evalua-
tion of ore agglomeration. As aforementioned by the former sec-
tions, the stripping and migration behavior of fine particles/
powders commonly occurred and became gradually severe along
with the saturated acid soaking process. As shown in Fig. 12a and
Eq. (1), Lewandowski quantitively describe the fine particles/
powders migration (after acid soaking process).
Mout
F¼  100%
M
10 mesh
Where F is the fine migration parameter, Mout is the total weight of
fine particles migrated out of ore agglomerations, M-10 mesh is the
total weight of
10 mesh fines available in ore agglomerations.
Generally, the dry strength was equivalent to the compressive
stress of dry agglomerations (after curing period), which tightly
influenced by the effect of overlying pressure on the structure
stability of agglomerated heaps (Nosrati et al., 2012b). Nosrati
tested the agglomeration mechanism (Fig. 12b). To further under-
stand the effect of compressive stress on the fracture and structure
failure, Wong et al. (1987) proposed the fracture/failure stress
calculation method of ore agglomerations, shown in Eq. (2).
2:8Pmax
sf ¼ (2)
pd2
Where sf is stress led to fracture and failure, d is diameter of
agglomeration.
3.2.3. Leachability
The majority objectives of agglomeration process were to
enhance the mineral grains liberation, create more chemical/bio-
chemical reaction interface and eventually obtain a higher copper
extraction rate (Johnson, 2018; Rawlings, 2002), Thus, in the
laboratory-scale studies, the saturated acid soaking test (single ore
agglomeration particle) and unsaturated column leaching (heaps
stacked by ore agglomeration particles) were commonly used to
evaluate the agglomeration leachability. The key evaluated pa-
rameters of pregnant leaching solution (PLS) was included of ion
concentration (e.g. Cu2þ, Fe2þ/Fe3þ, Ca2þ), pH value, oxidation
reduction potential (ORP), soluble oxygen concentration, and
mineralogy composition of ore agglomeration. To detect the
detailed chemical features in the leaching period, some chemical
analyses such as X-ray diffraction (XRD), scanning electron micro-
(1)
scope (SEM), Energy Dispersive Spectrometer (EDS) and Atomic
Force Microscope (AFM) were considered in the soak/column
leaching process (Palaniandy, 2015; Watling et al., 2014).
Currently, the contradiction between stable structure and better
leachability needed to be reconciled. For instance, the stucco binder
could play an efficient bonding effects, whereas excessive high-
content stucco could accelerate acid-proof substance layers via
 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705 11

Fig. 12. Mechanical tests in the wet/dry strength evaluation of agglomerations.

hydration reaction (such as calcium sulfate, etc.) and this undesir-
able acid-proof products layers prevented mass transfer and
extraction of internal valuable minerals (Lewandowski et al., 2010;
Lu et al., 2007). On the contrary, even though a low-content stucco
could obtain loose, porous layers and higher liquid retention, it
easily led to severe agglomeration disintegration, undesirable heap
compaction and weak leaching phenomenon.
3.3. Mass transfer and enhanced leaching mechanism
3.3.1. Mass transfer enhancement
The heap leaching was complex reacting system contained well-
developed pore structure, where types of masses co-existed,
including gas (e.g. soluble oxygen concentration), reaction fluid,
heat and microbial communities (Wang et al., 2020c). The exis-
tences of undesirable mass transfer and distribution were inferred
in the non-agglomeration heap (Bouffard and Dixon, 2009; Cross
et al., 2006; McBride et al., 2015; Nimmo et al., 2012; Ogbonna
et al., 2005): 1) gas (such as oxygen) could not reach the internal
of heaps and tend to escape along inter-particle paths even under
the assistance of enhanced aerations; 2) types of fluid flow (pref-
erential flow and matrix flow) co-existed and the liquid retention
gradually reached the steady state in the non-agglomerated heaps
once the irrigation condition was confirmed, it could lead to a
significant non-uniform of liquid distribution and potential blind
leaching regions (Fig. 13a); 3) the undesirable temperature
distribution that heat dissipated from the internal to the surface or
edges of heaps; 4) the proliferation and leaching ability of bacterial
community (e.g. Acidthiobacillus ferrooxidans (A.f) and Acid-
thiobacillus thiooxidans (A.t)) were tightly relied on condition,
where the oxygen and acidic ionic media were required. Owing to
the well-developed pore structure of agglomerated heaps, the mass
transfer process was further enhanced. Based on the previous
studies, the mass transfer was promoted from these following as-
pects (Carlesi et al., 2016; Delgado, 2006): 1) porous substance
layers of agglomeration (porous shell shown in Fig. 4a) could ob-
tained a better liquid retention and a higher mass fraction of sol-
uble ions; 2) pore structure (commonly quantified by porosity) in
agglomerated heaps was more uniform, which decreased the un-
timely formation of preferential flow and improved the liquid
saturation of heaps; 3) pivotal binders and additives (e.g. stucco,
cement, ferric chloride media, cupric chloride media, etc.) were
added in agglomeration preparation, which could ameliorate the
chemical reaction, biological activity and copper extraction rate by
mainly controlling the ORP and reaction activation energy. Besides,
in the gas-fluidized bed, it was also revealed that the agglomera-
tions were positive related to the mass transfer and leaching ki-
netics (Khalilitehrani et al., 2019).
3.3.2. Bio/chemical compaction
With the gradual dissolution of valuable minerals, the bio/
chemical compaction commonly appeared in agglomerated heaps,

Fig. 13. Flow behavior and bonding behavior in non-agglomerated/agglomerated heaps.

12 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705
especially in the high-saturated liquid condition. Since ore ag-
glomerations are structurally recombined via the crushing, bonding
and curing process, thus, the structure variation (e.g. spontaneous
bonding, compaction and sedimentation) could be easily observed,
especially under the undesirable PSD, binders and liquid distribu-
tion condition. This undesirable particle compaction could block
the flow paths and led to non-uniform liquid distribution (Orr,
2002). This bio/chemical compaction was mainly driven by bio/
chemical reaction and biological film attachments. With the in-
crease of saturated condition (Fig. 13b), the bio/chemical compac-
tion behaviors were basically divided into the pendular bonding,
funicular bonding, capillary bonding, droplet bonding (Mort, 2005).
The agglomeration particles disintegrated mainly due to the
dissolution of valuable minerals or alkaline gangue under acidic
solution erosion. It easily resulted in the disturbance of the heap
disintegration and compaction under the gravity of the overlying
granules and the surrounding stress (Chetty, 2018). In specific, in
terms of copper oxides, the heap compaction was mainly related to
the acidic consumed reaction and caused by the dissolution of
alkaline gangue minerals (e.g. CaSO4, etc.); in terms of copper sul-
fides (e.g. chalcopyrite, chalcocite, etc.), the leaching bacteria could
be pre-intervened in the preparation of agglomerations. As a
consequence, these microbial ecology and biofilm could accelerate
mineral dissolution (Yin et al., 2019). However, these bio-product
films composed of reaction products and bacteria could chroni-
cally attached on the surface or voids of mineral grains, which
potentially accelerated the bio/chemical compaction and led to a
lower permeability of agglomerated heaps.
3.3.3. Pre-treatment methods
The pre-treatments methods mean that some additives were
introduced in the preparing procedure before putting crushed feed
ores into agglomerated drums or conveyor belts. The pre-treatment
partially increased the cost due to crushing device, agglomeration,
binders and additives other procedures (Kodali, 2010). In terms of
copper sulfides, the acidic seawater-based media such as chloride
ion solution (e.g. acidic ferric chloride, acidic cupric chloride, etc.)
could be effectively utilized to dissolve the chalcopyrite and chal-
cocite (Hashemzadeh et al., 2019). This acidic ionic media could
improve the ORP and reaction activation energy of leaching system
without the intervention of bacterial community. The previous
studies showed that the high-content chloride ions solution was
added into ore agglomerated heaps using direct mixed or indirect
wetted methods. Besides, the crushing process and PSD were the
common controlling measures to adjust the agglomeration
enlargement. In terms of copper oxides with a high-mud content or
mixture minerals (copper oxides and sulfides), some porous
organic materials (e.g. straw, fiber rods) were also involved to
ameliorate bioleaching/leaching condition (Yin et al., 2019). This
type of additives could prevent the compactions caused by exces-
sive fine particles. Similarly, the fiber materials could also form
porous structure with many potential flow paths or pipes in
agglomeration. The hydrolysis reaction of fibers could produce
celluloses under acid solution condition, accelerating the formation
of sulfuric acid solution (Zhang et al., 2020). In this regard, the
additive of these straws could not only improve leaching efficiency,
but also realize the reuse and recycle of wastes crop straws, which
had a good potential to reuse the agricultural wastes in the
hydrometallurgy.
3.4. Dual-pore structure
3.4.1. Intra-/inter-particle porosity
The agglomeration was composed of powders, fine particle and
coarse particle. Conventionally, these void spaces were composed
of inter-particle pores and intra-particle pores in agglomerated
heaps. As shown in Fig. 4a, the potential paths of mass transfer, fluid
flow and oxygen migration appeared in unsaturated packed beds.
Types of pores co-existed in the single agglomeration particle,
including: 1) exposed pores (located in the surface of agglomera-
tion), 2) open pores (connected pores/paths between surface and
internal of agglomeration), and 3) closed pores (totally located in
the internal of agglomeration). Therefore, the dual-pore structure
should be seriously considered to leaching reaction. Due to porous
shells of agglomeration particles, the dual pore structure (inter-/
intra-particle porosity) was much better in the agglomerated heaps
instead of heaps packed by glass beads or crushed ores (Ilankoon
and Neethling, 2012a; Ilankoon, 2012).
Currently, the quantified descriptions of this dual-pore structure
were basically divided into two types: 1) using the mathematical
equation calculation to obtain parameters of the wet/dry bulk
density and total/wet porosity of packed bed; 2) using the X-ray
computed tomography (CT), micro CT (mCT) scanner and MATLAB to
obtain porosity distribution of agglomerated heaps (Lawrence and
Jiang, 2017; Lin et al., 2005). Commonly, the heap porosity using
realistic CT scanning and imaging algorithm methods were more
accurate than the experimental tests.
3.4.2. Minerals inlay and dual-pore porosity
Whether feed particles were agglomerated or not, the inlay
status of valuable copper mineral grains was various and basically
divided into five types (Rossi, 1990): 1) absolute exposure on the
ore surface, 2) direct exposure via pores or cracks, 3) indirect
exposure via pore or cracks only after leaching reaction, 4) partial
exposure via particle surface edges, 5) non-exposure and totally
located inside agglomerations. In ore heaps packed by copper sul-
fide minerals, different types of metal minerals (such as chalcopy-
rite, chalcocite, pyrite, etc.) simultaneously co-existed. Thus, this
complicated mineralogy inlay further extended the leaching period
(Anovitz and Cole, 2015). The undesirable distribution of mineral
grains negatively accelerated the minerals dissolution. In the
agglomerated heaps, the particle crushing and porous shells were
an easy approach to further exposed valuable mineral grains.
3.4.3. Leaching and dual-pores evolution
Notably, the compaction and distortion of pore structure were
not totally avoided both in agglomerated and non-agglomerated
heaps. Under the attacks of acidic leaching solution, some valu-
able metal mineral grains and alkaline gangue minerals gradually
dissolved and liberated from host ores in the leaching process
(Petersen and Dixon, 2003), which led to deformations (expansion
and compression) of intra- and inter-particle pores in agglomerated
heaps (Fig. 14b).
This porosity of agglomeration heaps was closely related to
leaching process (Hoummady et al., 2017). During acidic erosions of
leaching solution, the original surface bonding layers was gradually
destroyed and acid-proof layers of reaction products formed. Thus,
the porosity of agglomerated heaps continuously evolved, which
could be roughly expressed that: 1) the average porosity of upper
locations obviously increased due to the mineral dissolution and
downward migration of fine particles; 2) the average porosity of
middle locations roughly increased; 3) the average porosity of
bottom locations slightly increased or even potentially decreased
due to the fine particles deposition and compactions.
3.5. Flow behavior and percolation
3.5.1. Flow paths
Relied on the accepted opinions, heap leaching was unsaturated
leaching reaction system with dual-pore structure (Fig. 15a),
 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705 13

Fig. 14. 2-D CT image and 3-D reconstruction of pore structure of agglomeration (before and after leaching).

Fig. 15. Schematic of flow behavior and liquid hysteresis in the dual-pore packed beds.

wherein the flow paths were complicated and mainly included two
types: 1) preferential flow driven by gravity forces (Li et al., 2018);
2) diffusion flow driven by capillarity forces (Fernando et al., 2019,
2018). The ore particle segregation, particle stratification, even
inserted fine interlayers widely occurred in the non-agglomerated
heaps, (Wang et al., 2020a; Zhang and Liu, 2017). Owing to the
differences of PSD, solid density and rough surface, the acidic
leaching solution tended to flow into large-size pore throats, and
flow bypass packed beds with a lower permeability area (Fig. 4b).
The liquid spread condition of agglomerated heaps was obvi-
ously ameliorated due to well-developed intra- and inter-particle
pores. The liquid uniformly flowed downward instead of prefer-
ential flow in agglomerated heaps (Wang et al., 2020a). As a result,
the ameliorations effectively improve liquid diffusion in the intra-
particle pores, and avoid the undesirable bypass flow, preferential
flow or lower saturation regions. To better understand the flow
behavior, transient visualization technological methods have ob-
tained remarkable progresses, including X-ray CT, Magnetic Reso-
nance Imaging (MRI), Electric Capacitance Tomography (ECT),
Particle Image Velocimetry (PIV) and Particle Tracking Velocity
(PTV) and so on (Dhawan et al., 2012; Fagan et al., 2014; Liu et al.,
2009; Thaker et al., 2019; Yin et al., 2002). These visualized mea-
surements have promoted the understanding of flow behavior in
saturated/unsaturated packed bed at the meso- and even micro-
scale (Gvirtzman and Roberts, 1991). However, the mostly visual-
ized studies mainly focused on the liquid spread in unsaturated
heaps with poor intra-particle porosity (i.e. glass beads heaps,
crushed ore heaps), the studies of flow behavior in agglomerated
heaps with well-developed porosity were still not well known.
14 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705
Fig. 16. Industrial costs of major consumptions in the operation of agglomerated heaps.
3.5.2. Liquid retention and hysteresis behavior
The leaching solution was the important medium, which con-
tained the soluble oxygen, valuable metal ions, heat, and microbial
communities. Therefore, the liquid retention in unsaturated heaps
was tightly related to mass transfer and leaching efficiency
(Ahmadlouydarab et al., 2011). The immobile liquid and mobile
liquid co-existed in the preferential/matrix flow paths of unsatu-
rated heaps. The liquid retention of unsaturated heaps reached
steady state once the preferential flow paths formed, which means
that the liquid spreading became stable (Vethosodsakda et al.,
2013). The liquid retention in unsaturated heaps was quantita-
tively characterized via liquid holdup value, residual liquid holdup
value and relative liquid holdup. The (residual) liquid holdup of
unsaturated ore packed bed will increase if a higher irrigation rate
(or superficial flow velocity) was introduced; besides, the residual
liquid holdup was sensitive to agglomeration diameter while the
liquid holdup value was mainly affected by the irrigation condition
(Ilankoon and Neethling, 2012b).
The liquid hysteresis behavior was defined as the liquid was not
completely flow out of unsaturated packed bed after irrigation
(Fig. 15b), which led to the stagnant regions where the immobile
liquid reserved (Maiti et al., 2005). The liquid hysteresis behavior
was more obvious in agglomerated heaps where the inter- and
intra-particle pores co-existed. The hysteresis loop under different
irrigation condition commonly used to describe the liquid holdup
behavior in unsaturated ore packed bed. The liquid hysteresis was
less significant if the average porosity of agglomerated heaps was
lower, in which the preferential flow played a more dominated role.
Thus, the liquid hysteresis behavior directly affected by the irriga-
tion parameters and feed ores, resulting in the huge differences of
mass transfer, bio/chemical reaction and leaching efficiency.
3.5.3. Heap permeability
Heap permeability mainly controlled by the efficient porosity
directly influencing the flow behavior and steady liquid distribu-
tion. The undesirable heap permeability led to a poor Cu extraction
rate. Normally, the heap permeability was described by classic
equation of the soil mechanics and osmotic mechanics. In the dual-
pore structure of agglomerated heaps, the Darcy flow equation was
simplify used in the description of heap permeability, shown in Eq.
(3).
Q = A ¼ ðK DPÞ = mL (3)
Where K is the permeability (cm2), Q is the flow rate (cm3/s), A is
the area of cross section, DP is the pressure difference (rgh), r is
water density (0.001 kg/cm3), g is gravitational acceleration
(9.82 m/s2), DP/L is the water surface slope or gradient. To increase
the modelling accuracy, some optimized mathematical models
were also proposed to describe the flow behavior in unsaturated
heaps. For example, HeeCheneZhang Lattice Boltzmann Model
(LBM), the coupled Navier-Stokes and Brinkman’s equation,
improved vinegar & wellington calibration (CO2) and the trained
neural network (Lin et al., 2010; Miao et al., 2019, 2017a, 2017b)
were proposed and visualized the flow behavior. Besides, the
intervention of chemical binders and additives could improve the
hydraulic conductivity, increase the heap permeability, and
decrease the bulk density and reduce fine particle migration
(Chamberlin, 1986).
3.6. Commercial issues and controls
To date, the heap leaching and agglomeration technological
process have been widely utilized in the metal recovery from
copper oxides/sulfides, gold, and laterite nickel. There are around
90% copper and 71% gold produced by heap leaching in the North
and South America. According to Manning and Kappes (2005), the
majority costs of industrial operation could be divided into nine
parts (Fig. 16): surface/underground mining (26%), crushing (18%),
recovery plant (17%), agglomeration/stacking (14%), closure (7%),
support issues (6%), leaching operation (4%), site maintenance (4%)
and reagents (4%). In terms of the agglomeration process, the costs
of binders and additives was regarded as another pivotal issues in
the industrial operation. For instance, the average consumption of
cements is 10 kg/t. The agglomeration operating parameters should
be carefully confirmed based on the mining costs and minerals
quality. Moreover, due to the strict requirement of environmental
protection, the efficient removals of hazardous materials and acid
solution were thought as big deals to figure out (Bian et al., 2012).
The boundary control and case management were layout to avoid
the undesirable leakage of acidic leaching solution. In summary, the
optimization of operation costs should be carefully considered in
 L. Wang et al. / Journal of Cleaner Production 279 (2021) 123705 15

the agglomerated heaps, especially for the crushing, chemical detection methods devices (e.g. high-precision load cell, inser-
binders, recovery plant setup and agglomeration device. ted LabView software, etc.), calculation simulation software (e.g.
computational fluid dynamics (CFD), COMSOL Multiphysics,
4. Conclusion and prospect outlook etc.) were gradually invented. The potential effects of different
initial condition (e.g. irrigation rate/superficial flow velocity, ore
As an effective pretreatment method, ore agglomeration has particle size, initial moisture content, etc.) on the flow behavior
been widely introduced into the recovery of valuable mineral re- (e.g. liquid hysteresis and preferential flow paths) should be
sources, especially the high-mud minerals (e.g. laterite nickels, further explored. Moreover, as an additive pre-treatment pro-
copper oxides), and other valuable minerals that require this pre- cess, the operation costs of agglomerations preparations (e.g.
treatment to enhance the leaching reaction (e.g. secondary copper crushing process, binders/additives, environmental protection)
sulfides, laterite nickel, and uranium). should be also essentially considered in industrial agglomerated
In this paper, the key aspects of ore agglomerations related to heaps.
agglomeration preparation procedure, quality evaluation, mass
transfer and enhanced mechanism, dual-pore structure definition, Declaration of competing interest
flow behavior, percolation mechanism, commercial issues and
operation controls are carefully summarized and discussed. The The authors declare that they have no known competing
previous studies explicitly showed that the ore agglomeration financial interests or personal relationships that could have
method is a complexity process, mainly including: 1) physical is- appeared to influence the work reported in this paper.
sues (e.g. fine particle migration, compaction driven by gravity and
capillary forces, etc.), 2) chemical issues (e.g. reaction bonding us- Acknowledgements
ing chemical binders, etc.) and even 3) biological issues (e.g. mi-
crobial community and its species successions, etc.). In the The authors sincerely acknowledge financial supports from the
agglomerated heaps, these aforementioned issues are considered Key Program of National Natural Science Foundation of China (No.
and evaluated by extraction efficiency and production costs. Thus, 51734001), the Fundamental Research Funds for the Central Uni-
exploring a low-cost and high-efficient ore agglomerated method versities (No. FRF-TP-18-003C1, FRF-BD-19-001B), the National
was the key procedure in industrial cases. To realize this ultimate Science Fund for Excellent Young Scholars (No. 51722401) and the
purpose, this study proposed four prospects and potential studies: National Key Research and Development Program of China (No.
2016YFC0600704). Moreover, the authors emphatically clarified
❖ Exploring an efficient, low-cost binders or additives. Some that this critical review could not finished without the great sup-
chemical binders/additives still have technological obstacles ports from the references mentioned in this paper.
needed to consider before the industrial operations, such as
stucco (ore agglomerations mixed with massive calcium sulfate Abbreviations
were not conducive to subsequent leaching and costs), poly-
acrylamide (the potential environmental pollution risks, cost AFM Atomic Force Microscope
considerations and suitable minerals). Thus, accompanied with AHL Agglomerated Heap Leaching
the usage of new materials and waste materials (e.g. straws, CFD Computational Fluid Dynamics
etc.), some novel binders needed to be gradually innovated and DEM Discrete Element Method
eventually applied in industrial cases. The enhanced mechanism DL Dump Leaching
of binders/additives needed to depth understood. HL Heap Leaching
❖ Improving the description precision of dual porosity in HPGR High Pressure Grinding Rolls
agglomerated heaps. Previous studies and theories mainly LBM Lattice Boltzmann Model
focused on heap leaching with a weak intra-particle porosity ORP Oxidation Reduction Potential
(crushed ore, etc.), or soil mechanics where the diameter of feed PCB Printed Circuit Board
particles was much lower (laterite nickel ores). Due to the PLS Pregnant Leaching Solution
porous shell surrounded single agglomeration, the boundary PIV Particle Image Velocimetry
identification of adjacent agglomerations was very difficult and PTV Particle Tracking Velocity
required a higher precision or better optimization of imaging PSD Particle Size Distribution
algorithm. These potential studies included: 1) the dynamic MRI Magnetic Resonance Imaging
evolution of inter-particle and intra-particle porosity via the ISL In-Situ Leaching
undisturbed detection and 3-D reconstruction; 2) artificial VL Vat Leaching
controlling methods of pore structure to obtain a higher heap X-ray CT X-ray Computed Tomography
permeability and extraction efficiency. mCT Micro Computed Tomography
❖ Revealing the bonding mechanism of coupled physical, chemical
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