Minerals Engineering 142 (2019) 105934

Contents lists available at ScienceDirect

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

Tungsten extractive metallurgy: A review of processes and their challenges T

for sustainability
⁎
Leiting Shena,b, , Xiaobin Lia, Daniel Lindbergb, Pekka Taskinenb
a
Central South University, School of Metallurgy and Environment, Changsha 410083, China
b
Aalto University, School of Chemical Engineering, Metallurgical Thermodynamics and Modelling, Espoo 02150, Finland

A R T I C LE I N FO A B S T R A C T

Keywords: Tungsten, as a strategic and critical raw material, has a wide range of industrial applications, due to its re-
Tungsten concentrates markable physical and chemical properties and the difficulty in finding a viable substitution. Tungsten extractive
Secondary resources metallurgy produces the intermediate product from tungsten raw materials, intrinsically linking to the tungsten
Extraction technology industry across the supply chain stages. This paper critically reviews the tungsten extraction technologies and
Cleaner production
their challenges for the sustainability of tungsten metallurgy. The extractive metallurgy of tungsten has devel-
Waste management
Circular economy
oped for more than 150 years since 1847, and made a tremendous progress. The hydrochloric acid process is still
used in the industrial production to produce pure tungstic acid and metatungstic acid nowadays, but it is limited
by the formation of H2WO4 product layer in the decomposition. The current commercial tungsten extractive
metallurgy by soda/caustic soda digestion with solvent extraction or ion exchange step can use various raw
materials and obtain the uniform and high-quality product with a better energy efficiency, less labor and higher
tungsten yield. However, there also exist some disadvantages such as large amount of reagent consumption,
absence of chemical recycle, and discharge of large volumes of high-salinity wastewater. The recently developed
laboratory processes try to solve these problems, but some improvements are needed to increase the industrial
applicability. The optimized industrial process needs an overall consideration of the adoption of increasingly
complex raw materials, the recycle of aqueous solutions and chemicals, and the recovery of valuable substances
in processing circuit, as well as the practical policy. This paper contributes to better understanding the tungsten
extraction processes and developing a sustainable tungsten metallurgy in an environmentally friendly and
economical way.

1. Introduction
The population and economy growth in the world has generated an
urgent and increased demand for many metal commodities that were
previously not produced in large amounts. Especially, for such raw
materials, their supplies are essential to the everyday life, high-tech
products and emerging innovations. This situation has drawn a
worldwide attention by governments, industries and academics, for
whether the supplies of these raw materials will satisfy the growing
demand and whether the resource will become scarce or difficult to
obtain in the future. Thus, the criticality of such raw materials locally or
globally has become an important issue in the recent years (Tkaczyk
et al., 2018; Leal-Ayala et al., 2015).
Tungsten, as a strategical rare metal, is one of these critical raw
materials. It is an essential component in a wide range of products for
many end uses (Lassner and Schubert, 1999; Trasorras et al., 2016; BGS,
2011a; Gunn, 2014). Particularly, the use of tungsten in hard metals
represents its most important application. The industrial applications of
tungsten spread in metal-working, mining and stone-cutting tools, high
temperature technologies, lighting, catalyst and pigment, petroleum,
armaments and aerospace industries (Lassner and Schubert, 1999;
Trasorras et al., 2016; BGS, 2011a; Gunn, 2014; ITIA, 2011). All these
applications are contributed by the unique physical and chemical
properties of tungsten and its key compounds, such as high melting
point, low vapor pressure, high density, high tensile strength, low ex-
pansion coefficient, high wear resistance, high thermal and electrical
conductivity (Lassner and Schubert, 1999; Trasorras et al., 2016; BGS,
2011a; Gunn, 2014). Some of these properties make tungsten im-
possible to replace in certain specialized industrial applications
(European Commission, 2018). The selected characteristic properties of
tungsten and its application are summarized in Table 1.
Owing to the lack of viable substitutes in some applications,

⁎
Corresponding author at: Central South University, School of Metallurgy and Environment, Changsha 410083, China.
E-mail address: shenleiting@csu.edu.cn (L. Shen).

https://doi.org/10.1016/j.mineng.2019.105934
Received 12 June 2019; Received in revised form 13 August 2019; Accepted 13 August 2019
Available online 20 August 2019
0892-6875/ © 2019 Elsevier Ltd. All rights reserved.
L. Shen, et al.
Table 1
Selected special properties of tungsten and its applications (Trasorras et al., 2016; Gunn, 2014; BGS, 2011a; ITIA, 2011; Lassner and Schubert, 1999).
Special property
· Highest melting point of all metals, 3422 °C, after carbon in all chemical elements;
· Highest boiling point of all chemical elements, 5555 °C;
· Hardness, 7.5 for Mohs scale;
· Special heat capacity, 0.135 kJ·kg−1·K−1 at 25 °C, 0.17 kJ·kg−1·K−1 at 1000 °C,
0.2 kJ·kg−1·K−1 at 2000 °C;
· High density, 19254 kg/m3 at 25 °C, equal to that of gold, among the highest of all
metals;
· High tensile strength, 1000 MPa at 20 °C and ~100 MPa at 1650 °C;
· Low coefficient of linear thermal expansion, 4.5 * 10−6/°C;
· High thermal conductivity, 174 W/(m·°C);
· High electrical conductivity, 18.2 * 106 S/m.
tungsten is considered as strategic and critical in the supply chain of
raw materials by many countries or organizations (Calvo et al., 2019).
The European Union has started to get concerns on raw material supply
already some decades ago (European Commission, 1975), and updates
the list of critical raw materials almost every 3 years. 14 raw materials
were identified as critical in the 2010 report (European Commission,
2010). 20 commodities were considered critical in 2014 (European
Commission, 2014), and the critical number was last updated as 27
(European Commission, 2017). Tungsten was included in all of them.
Besides, the British Geological Survey classified tungsten as a very high
risk chemical element or element group in Risk list 2011, Risk list 2012
and Risk list 2015, with a supply risk index near to 10 (BGS, 2011b,
2012, 2015). The U.S. Geological Survey defined tungsten as one of
conflict minerals including tin, tantalum, tungsten, and gold, collec-
tively known as “3TG minerals” (USGS, 2014b). The EuChemS con-
sidered tungsten as the limited availability and future risk to supply
from conflict minerals (EuChemS, 2019). All these indicate the im-
portance of tungsten, particularly in the technologically-advanced
economies.
Tungsten does not occur in nature as an element, but in the form of
chemical compounds with other elements only (Liu and Ma, 1987).
Therefore, extractive metallurgy is of vital importance to supply the
intermediate product, mainly nowadays as ammonium paratungstate
(APT), in the tungsten industrial chain. This paper aims to give a critical
review on the current situation of tungsten raw materials, the devel-
opment and the state of the art of the tungsten extraction technologies.
Recommendations for the improvement direction in the industrial
processes will be discussed in detail for the sustainability of tungsten
extractive metallurgy.
2. Methodology and objectives
This article focuses on a comprehensive review of metallurgical
technologies for extracting tungsten from tungsten resources. The re-
lated information are collected from the available literature including
books, journal papers, patents and reports from the internet. The cur-
rent situation of raw tungsten resources, including primary ores and
secondary sources, used in industrial tungsten processes are critically
assessed. The development history of tungsten extractive metallurgy is
collected and reviewed. The problems and challenges of extraction
technologies in the current commercial processes are pointed out, as
well as these recently developed laboratory processes.
Recommendations for the improvement routes in the industrial pro-
cesses are made with accommodating the complex raw materials,
meeting the strict environmental requirements, and recycling valuable
substances in processing circuit for the sustainability of tungsten ex-
tractive metallurgy. Contents of this article may serve as useful source
Minerals Engineering 142 (2019) 105934
Main application
· 54% for Hard metals
Tungsten carbide (WC), important in the metal-working (40%), mining (30%), and
petroleum (20%) industries;
Cemented carbides, widespread applications in high tech tools, wear parts, mining and
stone-cutting tools, and engineering industry.
· 27% for Steel and other alloys
Special steel alloys, such as high-speed steels, heat-resistant steel and tool steel, utilized in
metal cutting and specialist engineering;
WCu and WNi alloys, and other tungsten alloys.
· 13% for Mill productions
Ref to tungsten wire, sheets or rods.
· 6% for Other application
Ammonium paratungstate, used as coloring agent;
Ammonium metatungstate, as chemical analysis or corrosion inhibitor;
WO3, as catalyst or pigment.
for the industry, investors, scientific community, and policy makers
regarding the profitable and environmentally friendly tungsten ex-
traction technologies.
3. Raw tungsten resources
The technological innovation cycles and the rapid growth of
emerging economies have led to a steadily increasing demand for
tungsten and its minerals. The future global demand may be double
between 2010 and 2030 (European Commission, 2018). The raw
tungsten material is the basis for tungsten extraction process, which
will influence the later metallurgical process. The tungsten raw material
used in the current commercial production includes primary resources
and secondary resources.
3.1. Primary resources
Although several tungsten-bearing minerals are known, most have
low or very low WO3 contents. The average abundance of tungsten in
the Earth’s continental crust is estimated to be 1.0 parts per million
(ppmw) (Liu and Ma, 1987; Rudnick and Gao, 2003). The concentration
in workable ores is usually between 0.1 and 1.0 percent tungsten tri-
oxide (WO3). Only scheelite (CaWO4, 80.5% WO3) and wolframite ((Fe,
Mn)WO4, 76.3–76.6% WO3) groups are abundant and rich enough to be
exploited in mineral engineering, which respectively account for 70%
and 30% of the resources (Gunn, 2014).
As shown in Fig. 1 a, based on the data by U.S. Geological Survey
(USGS, 2009–2018), the main reserves of tungsten locate in China
(~60%), Russia (~8%), US (~4%), Canada (~8%), Bolivia (~2%), and
other countries (~18%) including Austria, Australia, Mongolia, Spain,
United Kingdom, and Vietnam. Fig. 1 b shows the world tungsten mine
production by country in recent years (USGS, 2009–2019). The total
tungsten mine production increases stably due to the economy growth
especially in high tech and emerging innovations. The slight fluctuation
of tungsten mine production is influenced by political and environ-
mental features. China supplies more than 80% of tungsten mine pro-
duction in the world, even though it has about 60% of tungsten reserves
(Gunn, 2014).
The natural tungsten-bearing minerals need to be treated by mi-
nerals beneficiation to obtain a tungsten concentrate of around 65%
WO3. The WO3 content in tungsten concentrates is decreasing to 50% or
even lower nowadays, due to the increasingly complex tungsten re-
sources. With the progressive exhaustion of wolframite ore in last
several decades, scheelite, sometimes mixed with wolframite, is the
chief raw material to extract tungsten (Lassner and Schubert, 1999;
Trasorras et al., 2016). This makes the tungsten extraction process more
complex and challenging.
2
L. Shen, et al.
Fig. 1. The (a) estimated reserves 2009–2018 and (b) mine production 2008–2017 of tungsten in the world (data from USGS, 2009–2019).
Before entering into metallurgical processing, tungsten concentrates
need a pretreatment in order to stabilize the production, except the
high-quality concentrate. The pretreatment is usually carried out by
roasting at ~650 °C, leaching in a dilute inorganic acid or alkali solu-
tion, or combining of roasting and leaching process, in order to remove
organics and impurities in the ore (Trasorras et al., 2016; BGS, 2011a;
Zhang and Zhao, 2005).
3.2. Secondary resources
Recycling tungsten from scrap is another resource for tungsten
production, which can avoid the minimal costs, the chronic wastes and
serious environmental problems in mining and mineral processing
(Kieffer and Baroch, 1981; Bian et al., 2012). It is important for the
world’s tungsten supply, contributing to develop a sustainable, low
carbon, resource efficient and competitive economy (European
Commission, 2018). Tungsten scrap has been used as a secondary raw
material for production of pure tungsten since the 1960s, due to the
3
Minerals Engineering 142 (2019) 105934
high tungsten concentration (10–99%) in various types of scraps and to
a simultaneous recovery of other valuable constituents, such as Co and
Ta (Kieffer and Baroch, 1981).
There are various sources for tungsten containing scrap, which can
be classified as old scrap, new scrap and unrecovered scrap (BGS,
2011a; Gunn, 2014). The classification and their properties are pre-
sented in Table 2. New scrap, i.e., first-use products, is generated during
the processing of tungsten concentrates, chemicals and tungsten pro-
ducts. It is usually internally recycled in the processing. Old scrap, also
referred to as end-of-life scrap or end-use products, consists of tungsten-
bearing products that are no longer used. There are some tungsten
scraps not recoverable, due to the lack of an efficient collection system
or uneconomical recycling owing to contamination (BGS, 2011a; Gunn,
2014; Zeiler et al., 2018).
The flows of tungsten material in the tungsten industry is presented
in Fig. 2. Extractive metallurgy plays a key role in the industrial
tungsten chain. Two thirds of raw materials used in the tungsten ex-
tractive metallurgy are primary tungsten resources, and the rest is from
L. Shen, et al. Minerals Engineering 142 (2019) 105934

Table 2
Types of tungsten scrap and their properties (BGS, 2011a; Gunn, 2014).
Scrap types Description Tungsten content Estimated recovery

New scrap Generated during the processing of making metal powder,
carbide powder or chemicals, mainly in alloy industries.
Old scrap (a) Cemented carbide parts;
(b) Tungsten metal and tungsten alloy parts;
(c) Old superalloy scrap;
(d) Tungsten-bearing catalysts.
Unrecovered scrap Main in chemical applications (except for catalysts) for
lacking efficient collection or diseconomy.
10–99%, varying by its origin.
· Hard scrap (in lump form, e.g., sintered
material, scrap bar and sheet, wire), 10–98%;
· Soft scrap (finely divided material, e.g., powder,
dust, grindings, and turnings), 40–99.9%.
10–99%, according to its chemical application.
Very high (94–98%) by internal
recycling of the generated scrap.
~34%, varying greatly between
individual countries.
–

Fig. 2. The flowsheet of tungsten material in the tungsten industry (Trasorras
et al., 2016; Lassner, 1995).
secondary resources. Approximately 34% of total world tungsten supply
in 2013 was estimated from recycled sources (European Commission,
2014; Schubert and Zeiler, 2014). In some countries, this figure is much
higher, for example about 45% in Russia, and 50% in the USA and
Europe (Schubert and Zeiler, 2014).
4. Tungsten extraction technology
4.1. History of extraction technology
The tungsten extraction technology has been developed for more
than 150 years since Oxiland patented a method for producing sodium
tungstate, tungsten oxide, and metallic tungsten in 1847. Until the
1950s, the tungsten metallurgy was largely empirical and mainly based
upon patents (Li and Wang, 1955). With the development of industrial
technologies, the solvent extraction (SX) was used in the tungsten in-
dustry since 1959, and the ion exchange (IX) was adopted in the 1970s.
They speeded up the commercial progress of tungsten industry. Re-
cently, several novel laboratory processes have been proposed in order
to increase the tungsten recovery and adapt the strict environmental
requirements, including inorganic acid leaching with phosphor,
roasting transformation-(NH4)2CO3 leaching, and H2SO4 conversion-
ammoniacal (NH4)2CO3 leaching. The time line of the development of
tungsten extractive metallurgy is drawn in Fig. 3.
Almost all the available methods of treating tungsten ores have been
proposed before the 1950s. Li and Wang summarized the collected in-
formation of tungsten metallurgy in 1955 (Li and Wang, 1955), as well
as Qian in 1964 (Qian, 1964). The development of tungsten metallurgy
before the 1950s was compiled in Table 3, based on the reports by Li
and Wang (1955) and Qian (1964). These methods included roasting
with Na2CO3, NaOH, NaNO3 or neutral salts, Na2CO3 or/and NaOH
leaching, decomposing by H2SO4, HCl or HNO3, et al. It gives the
current foundation for the industrial production of tungsten.
4.2. Hydrochloric acid process
Based on the methods proposed before the 1950s, the process of
treating tungsten ores by hydrochloric acid or nitric acid has been es-
tablished, and hydrochloric acid was usually used in the industrial
production, as shown in Fig. 4. The hydrochloric acid decomposition
process is mainly employed to treat scheelite ores containing less im-
purities, in which the impurities are purified and separated from solid
H2WO4 during decomposition. The achieved H2WO4 is then directly
calcined to obtain WO3 product, or is re-dissolved in aqueous ammonia
to obtain ammonium tungstate solution for producing ammonium
paratungstate (APT) in the case of a high content of impurities in the
obtained H2WO4 (Yih and Wang, 1979; Zhang and Zhao, 2005). For the
treatment of wolframite ores or tungsten ores with a high impurity
content, the process becomes much more complex. A pure synthetic
scheelite is first produced through an alkali roasting or alkali digesting,
following chemical purification processes before the decomposition in
hydrochloric acid.
The hydrochloric acid decomposition process is still nowadays used
to produce pure tungstic acid and metatungstic acid in some industries.
A typical operation of hydrochloric acid decomposition includes
treating scheelite in a HCl solution with excess 1.5–3 mol to the stoi-
chiometric amount, at 85–100 °C (Martins, 2014).
4.3. Current commercial process
Compared to the hydrochloric acid process, the current commercial
production can use various raw materials with better energy efficiency
and less labor, for obtaining higher WO3 yield and uniform, high-
quality product (Trasorras et al., 2016). In the current industry prac-
tices, tungsten compounds are decomposed in a digestion process by
soda or/and caustic soda to produce soluble Na2WO4 and insoluble
carbonates or hydroxides. Then the impure Na2WO4 solution obtained
needs a purification and a conversion process to obtain pure ammonium
tungstate solution, following crystallization for producing APT (Gaur,
2006; Lassner, 1995). The main processes of alkali digestion following
with SX or IX step to convert sodium tungstate to ammonium tungstate
are shown in Fig. 5 and Fig. 6, respectively. In this paper, the digestion
and purification processes are described in detail, as a key for APT
production.
4.3.1. Digestion process
4.3.1.1. Caustic soda digestion. Caustic soda digestion is usually
employed to treat wolframite with a particle size < 44 μm in
concentrated NaOH solutions under atmospheric pressure, or in a
dilute NaOH solution by pressure digestion. Under atmospheric
pressure, a caustic soda solution with 40–50 wt% or 15 mol/L NaOH
is used at 100–145 °C to digest wolframite. The reaction time varies
from 0.5 h to 4 h, depending on the type of wolframite concentrate.
After finishing the reaction, the slurry is cooled to 90 °C and diluted by
water with the NaOH concentration reaching ~5 mol/L, in order to
dissolve solid Na2WO4. The WO3 leaching yield of 97–99% can be
obtained (Yih and Wang, 1979; Quatrini et al., 1982a; Quatrini and
Martin, 1982; Quatrini et al., 1982b; Quatrini, 1982). In the pressure
digestion, the operation takes place at 160–195 °C with the solid to
liquid ratio of 4–5 in a solution with excess ≥ 50% NaOH and reaction

4
L. Shen, et al. Minerals Engineering 142 (2019) 105934

Fig. 3. The history and development of tungsten extractive metallurgy.

time of 4 h; The total pressure is between 8 and 12 bar (Lassner, 1995).
Caustic soda can also be used to digest scheelite with a high
consumption of NaOH, but a simultaneous mechanical activation by a
thermo-milling process or a vibratory ball mill and an autoclave is
required in order to achieve high WO3 recovery. This technology is
adopted today mainly in China (Li et al., 1995; Sun et al., 2003; Zhao
et al., 2011a, 2011b, 2011c). In order to more easily extract tungsten
from scheelite, Gong et al. (2019) converted CaWO4 to MgWO4 by
roasting scheelite with MgCl2 before leaching the roasted product in
NaOH solution at 90 °C.
4.3.1.2. Soda digestion. Soda is typically employed for leaching
scheelite concentrate under pressure, particularly in Western World
plants. The process requires a large excess of reagent, but less gangue
dissolves in the solution. It can be carried out in mild steel autoclaves,
while NaOH treatment requires Inconel cladding (Maslenitsky, 1939;
Cho, 1988; Martins, 1996). Typical digestion conditions are 190–225 °C
temperature with total pressures of 12–26 bar in a 10–18% Na2CO3
solution and reaction time of 1.5–4 h; The stoichiometric ratio of Na2O
to WO3 is 2.5–4.5 (Yih and Wang, 1979; Lassner, 1995), but the ratio
increases even to 5 if scheelite concentration is low (Blair, 1966). The
surplus Na2CO3 would decrease the scheelite decomposition, due to the
formation of insoluble double carbonates (Na2CO3·CaCO3 or
Na2CO3·CaCO3) on the surfaces of scheelite particles (Martins and
Martins, 1997; Yang et al., 2018). Wolframite concentrates can also be
digested by soda under pressure, similarly to that for scheelite (Lassner,
1995).
Due to the increasingly complex mineralogy of tungsten ores, the
tungsten concentrate is usually a mixture of scheelite and wolframite.
So mixtures of soda and caustic soda are employed in the industrial
operation, where the soda to caustic soda ratio depends on the used
process and the assay of the concentrate. In addition, there are also
several processes for decomposing tungsten concentrates, such as soda/
caustic soda sintering-water leaching method (Paulino et al., 2012;
Srinivas et al., 2000), and NaF digestion (Zhang and Zhao, 2005). These
two methods are similar to the caustic soda and soda digestion, pro-
ducing a Na2WO4 solution. They, however, cannot meet the strict en-
vironmental requirements of the modern industry, due to the high en-
ergy consumption, corrosiveness and pollution by F– ion.
4.3.2. Solution purification
In the digestion process, some impurity elements presented as
gangue in the tungsten concentrate may dissolve in the solution. Thus, a
purification step is needed to keep the chemical quality of APT pro-
duction. Furthermore, the separation of sodium is carried out by SX or
IX step, along with converting Na2WO4 to (NH4)2WO4. The Na+

Table 3
Development of the tungsten metallurgy before the 1950s (Li and Wang, 1955; Qian 1964).
Methods Feature Production Starting time

Roasting with carbonates
Na2CO3 or/and NaOH leaching
Roasting with NaNO3
Alkali hydroxide decomposing
Ammonia decomposing
Decomposition with fused
alkali
Decomposition with bisulfate
Roasting with neutral salts
Acids decomposing
Others
Roasting tungsten ore with Na2CO3, then dissolving in water, following treatment by HCl H2WO4 1847
With or without pretreating by roasting, boiling the slurry of tungsten ore in Na2CO3 and H2WO4 1917
NaOH solutions or using an autoclave at high pressures, then treating the obtained solution or
tungstate precipitates by HCl/H2SO4
Roasting the mixture of NaNO3 and tungsten ores, together with carbon and slight NaSiO3 Na2WO4 solution 1924
solution, then leaching to obtain Na2WO4 solutions.
Decomposing wolframite or scheelite ore by caustic soda/potash in a digester, then using HCl H2WO4, CaWO4·H2O, or 1907
to precipitate H2WO4 tungstate solution
Ammonia solutions with or without ammonium carbonate or other ammonium salts treating Ammonium paratungstate 1928
tungsten containing materials under elevated pressure crystal
Treating scheelite or wolframite ore with excess fused NaOH (possible with slight lime), then K2WO4 /Na2WO4 solution 1912
leaching in water
Fused tungsten ore with alkali bisulfate H2WO4, or APT 1902
Roasting with NaCl, CaCl2, KCl, MgCl2, Na2SO4, K2SO4, KF or NaF in at around 900 °C H2WO4, WO3, Alkali tungstate 1920
Treating wolframite or scheelite by H2SO4, HCl or HNO3 in an autoclave, or bubbling SO2 gas H2WO4, WO3, or APT 1910
to the slurry of wolframite and water with heating
Separation as chloric Chlorides 1910
Decomposition by electrolysis Na2WO4 solution 1922
Decomposition by volatilization WO3 1931
As sulfide WS3 1925
With hydrogen sulfide Na2WS4 1922

5
L. Shen, et al. Minerals Engineering 142 (2019) 105934

Fig. 4. Hydrochloric acid process for APT production (Trasorras et al., 2016; Zhang and Zhao, 2005).

concentration must be reduced to < 10 mg/L, in order to produce the
high-quality APT and to avoid the problems during manufacturing of
metallic tungsten powder.
4.3.2.1. Solvent extraction. The solvent extraction process is widely
used in the tungsten industry, especially in Western World (Trasorras
et al., 2016; Yih and Wang, 1979). As shown in Fig. 5, the impurity
removal is first required. The impurities Si, P, Sn, As, and Fe are
removed from the Na2WO4 solution using magnesium salts and
ammonium hydroxide, forming precipitates. Subsequently, the
molybdenum removal is carried out by adding excess sulfide to
precipitate the molybdenum trisulfide in an acidified solution with
pH 2.5–3.0 (Hugginset al., 1982; Pastukhov and Skripchenko, 2015).
The Na2WO4 solution is acidified to pH 2.5–3.0 by an inorganic acid,
typically H2SO4, in order to increase the extraction efficiency in the
following solvent extraction step.
In the SX step, the organic phase is a mixture of tertiary or sec-
ondary aliphatic amines with isodecanol and kerosene (Cica et al.,
1990; Moris et al., 1999; Zhang et al., 2016). The extraction operation is
illustrated in Fig. 5. Tungsten is first extracted as isopolytungstate ions
in the organic phase, meanwhile the sodium is separated as a Na2SO4
solutions. Then the isopolytungstate is stripped by ammonia solution
into aqueous phase, forming ammonium isopolytungstate solution after
washing with deionized water. The organic solvent is regenerated by

Fig. 5. Current APT process with solvent extraction (Trasorras et al., 2016; Zhang and Zhao, 2005).

6
L. Shen, et al. Minerals Engineering 142 (2019) 105934

Fig. 6. Current APT process with ion exchange (Trasorras et al., 2016; Zhang and Zhao, 2005).

Fig. 8. The flowsheet of roasting transformation-(NH4)2CO3 leaching process.

Fig. 7. The flowsheet of H2SO4-H3PO4 leaching process (Zhao and Li, 2013).

washing with a dilute H2SO4 solution (Trasorras et al., 2016; Yih and
Wang, 1979). Molybdenum can also be removed from ammonium
tungstate solutions using solvent extraction with a quaternary ammo-
nium salt extractant (Wu et al., 2019).

4.3.2.2. Ion exchange. The IX process is mainly used in the plants in

China. A strongly alkaline ion exchange resin in the chloride form is
adopted in the industrial plant, including 201 × 7 type, WA type, and
D201 type (He, 1989; Kholmogorov et al., 1999; Zhao et al., 2010). The
IX step can not only convert Na2WO4 to (NH4)2WO4, but also remove Fig. 9. The flowsheet of H2SO4 conversion-ammoniacal (NH4)2CO3 leaching
impurities As, Si, V, P from the tungstate solution. Compared to SX step, process.
the IX step simplifies the operation of impurity removal, and only

7
L. Shen, et al.
Fig. 10. Tungsten recycling methods from the tungsten scraps (Srivastava et al., 2019; Shemi et al., 2018; Trasorras et al., 2016; BGS, 2011a).
removal of molybdenum is required by adding ammonium sulfide and a
copper compound to form copper thiomolybdate precipitate (Li et al.,
1995; Huang et al., 1995).
As demonstrated in Fig. 6, the impure Na2WO4 solution must be
diluted by softened or deionized water to a solution containing
15–25 g/L WO3, 4–8 g/L NaOH and < 0.7 g/L Cl–. When the solution is
in contact with the IX resin, tungstate is adsorbed; the process produces
large amounts of high salinity wastewater. Subsequently, the tungstate
is desorbed by washing the resin with ammonium chloride solution,
ammonium hydroxide and deionized water to obtain an ammonium
tungstate solution. The resin can be circulated and reutilized after the
stripping and cleaning steps.
4.3.3. Crystallization
The purified ammonium tungstate solution is crystallized via eva-
poration crystallization in the commercial APT production (Zhang and
Zhao, 2005; Gaur, 2006; Trasorras et al., 2016). During crystallization,
the purity of ammonium tungstate solution and crystallization para-
meters are the key to produce high-quality APT, which will influence
the size and morphology of APT crystals. A further separation of im-
purities from APT product is achieved after crystallization, with mother
liquor recycling back in the process.
The three major intermediate compounds, ammonium metatung-
state, yellow oxide and tungsten blue oxide, are produced from APT
through the thermal decomposition (Gaur, 2006; Kalpakli et al., 2013).
The tungsten powder can be produced by reducing tungsten trioxide
with hydrogen (Jiang et al., 2019), ethanol (Cetinkaya and Eroglu,
2017) and methane (Cetinkaya and Eroglu, 2015; Wu et al, 2018).
As the crystallization and subsequent operations are almost the
same in the commercial production, this paper does not give details of
these steps.
4.4. Recent development
In order to more efficiently and more economically extract tungsten
from its increasingly complex tungsten raw materials, there are several
laboratory-scale attempts to explore a novel process for tungsten ex-
traction.
4.4.1. Acid leaching with phosphor
In order to increase the WO3 recovery obstructed by the formation
of H2WO4 product layer in hydrochloric acid process, Xuin et al. (1986)
treated scheelite by hydrochloric acid in the presence of phosphoric
acid as a complexing agent, obtaining soluble H3PW12O40 and CaCl2;
8
Minerals Engineering 142 (2019) 105934
They also studied kinetics of the decomposition process. Gürmen et al.
(1999, 2002) used a mixture of hydrochloric acid and phosphoric acid
to decompose scheelite, and then precipitated a hetero-polytungstate
salt (NH4)3·PW12O40·9H2O by adding NH3·H2O or NH4Cl. They obtained
WO3 powder by calcination of the precipitated salt, and finally pro-
duced metallic tungsten powder by reduction of WO3. The acid solution
can be recycled back to leaching by treating of CaCl2 with H2SO4 and
forming gypsum. Kalpakli and Yusufoglu studied leaching kinetics of
synthetic CaWO4 in the HCl and H3PO4 solutions (Kahruman and
Yusufoglu, 2006) and oxidation kinetics of phosphotungsten suboxide
(Kalpakli and Yusufoglu, 2007). Kalpakli et al. (2012b) further de-
termined the thermal decomposition mechanism of ammonium phos-
photungstate hydrate in air.
Aiming to avoid the treatment of CaCl2 solution, Razavizadeh and
Ershad (2006) proposed a new process for leaching low-grade or high-
grade scheelite ores by H2SO4 solution in the presence of H3PO4 and
NaCl at atmospheric pressure, producing soluble tungstic acid solution
and solid CaSO4·2H2O; The precipitation of (NH4)3P2O4·4WO3·9H2O
was obtained by adding NH4Cl in the leaching solution. Then the pre-
cipitation of (NH4)3P2O4·4WO3·9H2O was dissolved with ammonium
hydroxide, followed by solution purification. The purified solution was
evaporated at 200 °C to obtain APT which can be further calcined to
WO3 and reduced to metallic tungsten powder.
Li and Zhao (2016) used a mixed solution of H2SO4 and H3PO4 to
digest scheelite concentrate, and applied a patent (Zhao and Li, 2013)
based on this method. Its flowsheet is shown in Fig. 7. The process is
similar to that of Razavizadeh and Ershad (2006). The phosphotungstic
acid crystal is first obtained from the leaching solution through a
cooling crystallization or concentrating crystallization process. Then it
is dissolved in water, and the transformation is carried out by adding an
ammonia solution, or using the IX or SX step (Yang et al., 2016).
Additionally, Martins leached synthetic scheelite in hydrochloric
acid (Martins et al., 2003) or nitric acid (Martins, 2003) with pH of
1.5–3.0 in a temperature range of 25–100 °C to obtain soluble meta-
tungstates. Potashnikov et al. (1970) and Kalpakli et al. (2012a) used a
relatively expensive oxalic acid to attack scheelite, by forming soluble
hydrogen aqua oxalate tungstate (H2[WO3(C2O4)H2O]) and solid
CaC2O4. He et al. (2014) leached the scheelite in a hydrochloric acid
solution containing hydrogen peroxide as a complexing agent to pro-
duce soluble peroxotungstic acids [WO(O2)2(H2O)2]. However, there
are no follow-up reports about the subsequent processes of treating the
soluble metatungstates, soluble hydrogen aqua oxalate tungstate or
peroxotungstic acid solutions.
L. Shen, et al. Minerals Engineering 142 (2019) 105934

4.4.2. Roasting transformation-(NH4)2CO3 leaching

Yield between 97 and 99%; Na2CO3·CaCO3 or

Li et al. (2014a, 2014b) proposed a novel technology for tungsten

recovery; Product quality depending on raw

High volatility and corrosion; Low WO3 extraction by roasting transformation-(NH4)2CO3 leaching, in order to
achieve a recycle of raw materials and to avoid discharge of waste-

More auxiliary material consumption

water. The flowsheet of the technology is shown in Fig. 8. In this ap-
Yield between 97 and 99%
proach, the well-mixed raw material of tungsten concentrate and cal-
cium carbonate is roasted at 800–850 °C to convert tungsten minerals to
Na2CO3·2CaCO3 may form Ca3WO6 (Li et al., 2015) and/or Ca3−x(Fe, Mn)xWO6 (0 < x ≤ 1) (Li
et al., 2016); Subsequently, the roasted product is leached in ammo-
nium carbonate solution at 30–80 °C to obtain (NH4)2WO4 solution (Xu
et al., 2019). The leaching residue is mainly of calcium carbonate,
materials

which can be recycled. The purified leaching solution is evaporated and

Others

crystallized for producing APT. The mother liquid together with sup-
plementary ammonium carbonate is recycled back to the leaching step.
Only mother liquor

Only mother liquor

Solvent recycling

4.4.3. H2SO4 conversion-ammoniacal (NH4)2CO3 leaching

Resin recycling
No recycling

Considering the negligible volatility and low cost of sulfuric acid

Recycling

recycling

recycling

and the easy recycling of ammoniacal ammonium carbonate solution, a

novel process for producing ammonium paratungstate in an more effi-
cient, more economic and cleaner manner was proposed recently
through sulfuric acid conversion-ammoniacal ammonium carbonate
> 80 t-high salinity wastewater/t-
High salinity wastewater; Alkaline
leaching residue with < 3% WO3

Leaching residue with ~1% WO3

High salinity acidic wastewater;

leaching route. It features circulation of the leaching reagents and by-

passes the conversion of Na2WO4 to (NH4)2WO4. Its flowsheet is shown
> 25 t high salinity acidic
High salinity wastewater;

in Fig. 9. A complete conversion of tungsten concentrates in H2SO4

solutions can be achieved at 70–90 °C under atmospheric pressure by
wastewater /t-APT

controlling H2SO4 concentration (Li et al., 2017; Shen et al., 2018b) and
oxidizing the Fe2+/Mn2+ in the solution (Shen et al., 2018c); The
Discharge

converted solution with only slight amounts of metal ions can be re-
circulated to treat the next batch of tungsten concentrate by adding
APT

H2SO4. The converted product, a mixture of H2WO4 and CaSO4, is then

leached at ~30 °C under atmospheric pressure in an ammoniacal
12–26 bar pressure; Chemical cost higher than Na2CO3
> 1.6 stoichiometric ratio NaOH; Normally ≥ 100 °C;

2.5–4.5 stoichiometric ratio Na2CO3; 190–225 °C with

(NH4)2CO3 solution to directly obtain (NH4)2WO4 solution and solid

CaCO3 in the leaching residue (Shen et al., 2018d). The APT production
can be obtained from the evaporation-crystallization of purified
(NH4)2WO4 solution; After APT crystallization, the residual WO3 in the
mother liquid is precipitated as solid H2WO4 by adding H2SO4, which
can be recycled back to the leaching step; The leaching system can be
2–2.5 stoichiometric ratio HCl

recovered by absorbing gaseous NH3 and CO2 from the evaporation-

crystallization step and recovery process step.
0.54–1.3 t-H2SO4/t-APT;
80–125 t-H2O/t-APT
Need diluted water

> 25 t-H2O/t-APT;

4.5. Recycling tungsten from scrap

Consumption

With the progressively complex tungsten minerals and the depletion

of limited natural resources, recycling tungsten from scrap is of in-
creasing importance for the worldwide tungsten industry and its sus-
tainability. There are lots of research carried out on the recycling
methods in recent years, to improve the recycling recovery of tungsten.
Various raw materials, more

Various raw materials, more

Scheelite concentrates with

As summarized in Fig. 10, the recycling methods can be divided into

suitable for wolframite

direct recycling, semi-direct recycling, and indirect recycling methods

suitable for scheelite

(Trasorras et al., 2016; BGS, 2011a; Shemi et al., 2018).

The direct recycling is converting tungsten scrap to powder in an
The state of the art of current industrial processes.

less impurities
Raw materials

environmentally and economically beneficial manner. A typical method

is recycling cemented carbide scrap with the Zinc-melt process to re-
cover WC-Co, with no consumption of chemicals, which obviously re-
–

duces both the atmospheric and chemical waste pollution (Trent, 1946;
Barnard, 1971; Freemantle and Sacks, 2015). However, only limited
Soda digestion

types of scrap can be recycled directly.

With solvent
Caustic soda

extraction

The semi-direct recycling is suitable for low grade scrap containing

exchange
digestion

With ion

other metals. A typical method is the selective acid leaching: The

tungsten scrap is first leached in a mineral or organic acid to dissolve
the binder metal, then leaching the remainder in another solution to
Classical process

Modern process

recovery tungsten and other metals (Chio et al., 2018; Edtmaier et al.,
2005; Song et al., 2018; Zhang et al., 2018). The resulting powder is
closely related to the scrap type and the recycling method.
Process
Table 4

The indirect recycling is sometimes called hydrometallurgical re-

cycling. The fused or oxidized tungsten scrap is treated through the

9
L. Shen, et al.
Fig. 11. The material and energy flows in the current tungsten extractive metallurgy.
modern tungsten extraction metallurgical process to obtain APT or
H2WO4 production (Bhosale et al., 1990). This method can treat most
tungsten scrap, but is in an expensive, involving high chemicals con-
sumption and waste-producing procedures.
5. The state of the art
As science and technology develop, the tungsten metallurgy in-
dustry has achieved a great progress, along with the growing produc-
tion. However, there still exist many problems and challenges in the
current tungsten industry. In order to clarify the state of the art of the
tungsten extraction processes, the adoption of tungsten raw materials,
the consumption of chemicals and auxiliary materials, water and en-
ergy, the discharges of wastewater, solid residues and exhaust gas, and
the production cost were considered in the assessment of their ad-
vantages and disadvantages, as well as the recycling of raw material,
other metals and water in the process.
5.1. Current industrial practices
Table 4 summarizes the state of the art of the current industrial
processes, including the hydrochloric acid decomposition process and
the soda/caustic soda digestion with SX or IX.
5.1.1. Hydrochloric acid process
Acid decomposition method has a short process flowsheet with low
product cost. But it is usually used to treat scheelite concentrates con-
taining less impurities. When treating scheelite concentrate with high
impurity contents or wolframite concentrate, the process becomes more
complex and meets difficulties to obtain the high quality of production.
Some impurities, such as phosphorus and arsenic, may react with solid
tungstic acid and form soluble heteropolytungstic acid. Thus, a pre-
treatment of the concentrates is required to remove these impurities.
Additionally, the strong volatility and corrosion of hydrochloric acid
will result in a bad operation environment and a high investment cost.
From a thermodynamic point of view for the decomposition, the
equilibrium constant for the reaction of scheelite in hydrochloric acid
solutions is large, with a value about 1.0*104 at 25 °C (Martins, 2014;
Shen et al., 2018a), and solubility of H2WO4 in the acid solution is very
small (EL Wakkad and Rizk, 1956). Thus, the conversion of scheelite to
tungstic acid can be completed thermodynamically. Whereas, the con-
version of scheelite to tungstic acid is often not high, as the produced
solid tungstic acid covers the surfaces of scheelite particles and blocks a
10
Minerals Engineering 142 (2019) 105934
further reaction of HCl with CaWO4 particles, decreasing the tungsten
recovery. Many studies have been carried out to improve this situation,
including reducing the particle size (Fieberg and Coetzee, 1986), using
a large excess of concentrated HCl (Vezina et al., 1970), and utilizing
heated ball mill reactors (Meerson and Khavskii, 1961), and the use of
organic acids to dissolve tungstic acid (Davey, 1990). These measures
can eliminate the undesired effect of solid H2WO4 layer, whereas they
will increase the production costs or require expensive equipment with
corrosion resistant materials.
5.1.2. Current commercial process
The current process can use different types of raw materials, obtain
a higher yield and an uniform high-quality product. However, its dis-
advantages are also very obvious, as shown in Fig. 11. Both soda and
caustic soda digestions require excess amounts of reagents and elevated
temperature in an autoclave to achieve a high WO3 recovery. The ex-
cess NaOH and/or Na2CO3 are hard to recycle as the leaching solution is
a mixture of Na2WO4 with large amount of NaOH and/or Na2CO3. The
obtained sodium tungstate solution is then converted to ammonium
tungstate after the purification by a SX or IX step. It simultaneously
generates sodium chloride or sodium sulfate solution and thus con-
sumes a lot of soda or caustic soda (Trasorras et al., 2016). The recovery
of NaOH and Na2CO3 from the leaching solutions has been studied
using crystallization or ionic membrane methods (Zhang and Zhao,
2005), but they result either in a strong WO3 loss or in high cost of the
process. The WO3 content in the leaching residue is about 1–3 wt%,
which is much higher than that of natural ores. However, there is no
information about the recovery of tungsten from this residue, as well as
the recoveries of valuable substances like molybdenum in the proces-
sing circuit. About 4% WO3 loss in the modern APT production was
pointed out by Leal-Ayala et al. (2015).
In addition, when using the SX step, more auxiliary chemical re-
agents are used to remove the impurities from the raw Na2WO4 solu-
tion; The acidification of Na2WO4 solution is carried out by adding a
large amount of H2SO4. About 25 tons water is consumed for per ton
APT production in the SX step, together with the discharge of the al-
most same volume wastewater containing Na2SO4 (Furberg et al.,
2019). The purification operation becomes much shorter with an IX
step, but huge water is still used to dilute the Na2WO4 solution before
the ion exchange, to desorb the tungstate from the resin and to wash the
resin for reuse. There is a consumption of about 120 tons water during
the IX step, whilst it discharges 96 tons wastewater for per ton APT
production (Ma et al., 2017).
L. Shen, et al. Minerals Engineering 142 (2019) 105934

Wan et al. (2012) pointed out that the amount of high-salinity

Consumption of H3PO4; Accumulation of

material; Possible complex purification

Accumulation of impurity elements in

wastewater discharged for per ton APT production was ~20 and 100

impurity elements in acid solutions

Burdensome recycling for auxiliary

tons for the SX and IX steps, respectively. The later value was even
reported as ~126 tons for IX process (Wan et al., 2015a, 2015b). Ob-
viously, the caustic soda or soda process raises the production cost, and
especially leads to serious environmental pollution.

5.2. Recently developed laboratory process

acid solutions
Others

The recently developed laboratory process tries to avoid the dis-

steps

charge of large amount of high-salinity wastewater and the conversion

of sodium tungstate to ammonium tungstate. The state of the art for
Auxiliary material recycling

Aqueous solution recycling;

these recently developed processes is presented in Table 5.

Leaching agents recycling;

Leaching agents recycling

The H2SO4-H3PO4 leaching technique uses stoichiometric amount of

Recycling spent acid

H2SO4 and H3PO4 with the recycling of the spent acid solution, and
obtains an ammonium tungstate solution containing phosphorus, by
dissolving the phosphotungstic acid crystal with ammonia solution.
Recycling

However, the separation of phosphorus from ammonium tungstate so-

solution

lution should be carried out by magnesium salt precipitation, IX, or SX.

Thus, it will consume a large amount of magnesium salts for the pre-
cipitation or huge volume of water for IX or SX step. Thus, they result in
CaSO4·2H2O; CO2; Wastewater

discharge of solid waste or wastewater containing phosphorus. The

or solid waste containing P

impurity elements in the concentrates may dissolve and accumulate in

the acid solutions, and causes difficulties in the continuous recycling of
the acid solutions. As reported, this process is only used to treat
scheelite concentrates.
CaSO4·2H2O
Exhaust gas

Roasting transformation-(NH4)2CO3 leaching process aims at

Discharge

achieving the zero-waste discharge with a “closed circulation” route,

and can treat various tungsten raw materials. However, the roasting
process involves a high energy consumption and discharges exhaust
(NH4)2CO3; Some CaO, Ca(OH)2 or CaCO3, and

gas. The stoichiometric ratio of CaO to WO3 in the feed mixture reaches
recycling; NH3·H2O; large amount magnesium

about 3, and results in a cumbersome recycling for the auxiliary ma-

High energy consumption; Stoichiometric
Stoichiometric H3PO4 and H2SO4 due to

terials. Many impurities after roasting at high temperatures may dis-

solve into the leaching solution, leading to a complex solution pur-
ification step.
H2SO4 conversion-ammoniacal (NH4)2CO3 leaching process can
treat scheelite, wolframite and mixed concentrates. The spent H2SO4
Stoichiometric H2SO4

solution can be recycled with a supplement of H2SO4 so that solid

CaSO4 and H2WO4 are formed in the conversion process, but the Fe2+/
Mn2+ and other impurity elements would accumulate when treating
salts or water

additive CaF2
Consumption

wolframite and complex low-quality concentrates. Additionally, the

efficiency of recovering the leaching system needs a further detailed
study. Some additional measures are required to solve these problems.
These three recently developed processes make a noticeable tech-
nical progress in the extractive metallurgy of tungsten, with the con-
concentrates, more suitable for

sumption and recycling of chemical reagents. However, they need large

Adoption of raw materials

scale industrial piloting to increase the applicability, as well as for

Scheelite and wolframite

improvements in the process flowsheet.

Scheelite concentrates

Various raw materials

5.3. Tungsten scrap recycling

The state of the art of recent developed processes.

scheelite

Recently, Shemi et al. (2018) and Srivastava et al. (2019) reviewed

the recycling tungsten from carbide scrap and spent tungsten materials,
and analyzed in detail the advantages and disadvantages of each
Roasting transformation-(NH4)2CO3

method. So, this paper does not review them one by one again, but
gives our own opinion of the tungsten recycling.
H2SO4 conversion-ammoniacal

The classification of scraps with various types should be carried out

firstly, as well as a thorough consideration of efficiency, costs and en-
(NH4)2CO3 leaching
H2SO4-H3PO4 leaching

vironmental impact of the recycling. In addition, as Reck and Graedel

(2012) pointed out, the positive politics, increased collection and
classification of different types of tungsten scraps, and the deployment
leaching

of recycling methodology can enhance the tungsten scrap recycling.

Importantly, the recycling process should take full advantage of the
Process
Table 5

existing equipment in the industry, due to the expensive investment of

new product line.

11
L. Shen, et al.
Fig. 12. The scope of a sustainable tungsten extractive metallurgy.
6. Conclusions and recommendations
The supply of tungsten is essential for the production of many goods
and appliances used in everyday life, where tungsten extractive me-
tallurgy is intrinsically linked with the tungsten industry across all
supply chain stages. The world tungsten mine production increases with
a constant rate every year, but the tungsten raw materials become more
complex due to the progressive exploitation of high-quality con-
centrates and the adoption of various types of tungsten scraps. This
makes the tungsten extraction process more complex and challengeable
in terms of the sustainable production.
The extractive metallurgy of tungsten has developed since 1847,
and has achieved a great progress. Until the 1950s, the tungsten me-
tallurgy was largely empirical and mainly based upon patents, even
though almost all the currently available methods of treating tungsten
ores have been proposed at that time. Since then, the hydrochloric acid
decomposition process has been used in the industrial production, and
it still is used to produce pure tungstic acid and metatungstic acid
nowadays. The process is limited by the formation of solid H2WO4
product layer in the decomposition, resulting in a low WO3 recovery.
The current commercial extractive metallurgy by soda/caustic soda
digestion with solvent extraction or ion exchange step can use various
raw materials with better energy efficiency, less labor, higher WO3
yield, and yielding uniform and high-quality tungsten product.
However, there exist some obvious disadvantages in this industrial
method, such as ≥2.5 stoichiometric ratio of reagent consumption,
absence of recycling the aqueous solutions and chemical reagents, and
discharge of high-salinity wastewater about 25 or 100 tons/ton-product
for solvent extraction and ion exchange steps, respectively.
The recently developed laboratory-scale processes aims at solving
the problems existing in the current commercial production, but some
improvements are needed to increase the applicability for a more suc-
cessful industry applications.
For the recycling of tungsten scrap, the increased collection and
classification of different types of tungsten scraps should be carried out
in order to enhance the tungsten recycling. Under an overall con-
sideration of efficiency, costs and environment impact, the recycling
12
Minerals Engineering 142 (2019) 105934
process should take full advantage of the existing equipment in the
industry, due to the expensive capital investment of line.
Therefore, the sustainable extractive metallurgy of tungsten should
include the following features (Fig. 12): (1) The process adapts varying
types of tungsten raw materials, including scheelite, wolframite, mixed
concentrates and different tungsten scraps; (2) The process uses less
reagents, water and energy, minimizing recycling of aqueous solutions
and raw materials; (3) The process recycles the aqueous solutions and
chemicals, and minimizes the waste discharge and utilizes the resources
in the waste; (4) The process has an overall consideration of practical
policy and appropriate technology (Wigginton et al., 2012).
The contents in this article may serve as useful source for the in-
dustry, investors, scientific community, and policy makers regarding
profitable and environmentally friendly tungsten extraction technolo-
gies. The different evaluations, like environmental life cycle assessment
(Ma et al., 2017; Furberg et al., 2019), should be further carried out for
the processes in extractive metallurgy of tungsten to point out in detail
the sustainable actions. Thus hopefully, it will affect the sustainability
of the tungsten extractive metallurgy in an environmentally friendly
and economical manner.
Acknowledgements
The first author gratefully acknowledge the financially supports
from EDUFI Fellowship TM-18-10745 for his exchange and doctoral
study and from Aalto CHEM Funding (Project 902222) for the final
stage of doctoral study in Aalto University, Finland.
References
Barnard, P.G., 1971. Reclamation of refractory carbides from carbide materials. US Patent
No. 3,595,484.
BGS, 2011b. Risk List 2011. British Geological Survey, Keyworth, UK.
BGS, 2011a. Tungsten. British Geological Survey, Keyworth, UK.
BGS, 2012. Risk List 2012. British Geological Survey, Keyworth, UK.
BGS, 2015. Risk List 2015. British Geological Survey, Keyworth, UK.
Bhosale, S.N., Mookherjee, S., Pardeshi, R.M., 1990. Current practices in tungsten ex-
traction and recovery. High Temp. Mater. Processes 9 (2–4), 147–162.
Bian, Z.F., Miao, X.X., Lei, S.G., Chen, S.E., Wang, W.F., Struthers, S., 2012. The
L. Shen, et al.
challenges of reusing mining and mineral-processing wastes. Science 337 (6095),
702–703.
Blair, B., 1966. Process of recovering high purity tungsten compositions from tungsten-
bearing ores. U.S. Patent 3,256,057.
Calvo, G., Valero, A., Valero, A., 2019. How can strategic metals drive the economy?
Tungsten and tin production in Spain during periods of war. Extractive Industries
Soc. 6, 8–14.
Cetinkaya, S., Eroglu, S., 2015. Thermodynamic analysis and reduction of tungsten tri-
oxide using methane. Int. J. Refract. Met. Hard Mater. 51, 137–140.
Cetinkaya, S., Eroglu, S., 2017. Reduction of tungsten trioxide with ethanol. Int. J.
Refract. Met. Hard Mater. 64, 184–189.
Chio, I.H., Moon, G., Lee, J.Y., Jyothi, R.K., 2018. Extraction of tungsten and vanadium
from spent selective catalytic reduction catalyst for stationary application by pressure
leaching process. J. Clean. Prod. 197, 163–169.
Cho, E.H., 1988. Kinetics of sodium carbonate leaching of scheelite. JOM 40 (7), 32–34.
Cica, J., Diez, F.V., Moris, M.A., 1990. Solvent extraction of molybdenum and tungsten by
Alamine 336 and DEHPA. Hydrometallurgy 25, 125–135.
Davey, T.R.A., 1990. Method of extracting tungsten values from tungsten containing ores,
U.S. Patent 4,9100,00.
Edtmaier, C., Schiesser, R., Meissl, C., Schubert, W.D., Rock, A., Schoen, A., Zeiler, B.,
2005. Selective removal of the cobalt binder in WC-Co based hard metal scraps by
acetic acid leaching. Hydrometallurgy 76, 63–71.
EL Wakkad, S.E.S., Rizk, H.M., 1956. The solubility of tungsten trioxide in hydrochloric
acid. J. Chem. Soc 3248-3248.
EuChemS, 2019. The 90 natutal elements that make up everything. IYPT 2019. www.
euchems.eu.
European Commission, 1975. The Community’ supplies of raw materials. Communication
from the Commission to the Council. COM (76) 50 Final. European Commission.
European Commission, 2010. Critical raw materials for the EU. Report of the Ad-hoc
working group on defining critical raw materials. European Commission.
European Commission, 2014. Report on critical raw materials for the EU, Report of the
Ad-hoc working group on defining critical raw materials. European Commission.
European Commission, 2017. Study on the list of critical raw materials for the EU. Critical
Raw Materials Factsheets. European Commission.
European Commission, 2018. Report on Critical Raw Materials and the Circular Economy.
Raw Materials. DOI: 10.2873/167813.
Fieberg, M.M., Coetzee, C.F.B., 1986. The recovery of tungsten from South African low-
grade scheelite concentrates, Mintek, Report No: M164D. Council for Mineral
Technology, pp: 1–22.
Freemantle, C., Sacks, N., 2015. Recycling of cemented tungsten carbide mining tool
scrap. J. South Afr. Inst. Mining Metal. 115, 1207–1213.
Furberg, A., Arvidsson, R., Molander, S., 2019. Environmental life cycle assessment of
cemented carbide (WC-Co) production. J. Clean. Prod. 209, 1126–1138.
Gaur, R.P.S., 2006. Modern hydrometallurgical production methods for tungsten. JOM
58, 45–49.
Gong, D.D., Zhou, K.G., Peng, C.H., Li, J.J., Chen, W., 2019. Sequential extraction of
tungsten from scheelite through roasting and alkaline leaching. Miner. Eng. 132,
238–244.
Gunn, G., 2014. Critical Metals Handbook, Chapter 16, Tungsten. British Geological
Survey/American Geophysical Union/John Wiley & Sons, Ltd., pp. 385–413.
Gürmen, S., Timur, S., Arslan, C., Duman, I., 1999. Acid leaching of scheelite concentrate
and production of heteropoly-tungstate salt. Hydrometallurgy 51, 227–238.
Gürmen, S., Timur, S., Arslan, C., Duman, I., 2002. Production of pure tungsten oxide
from scheelite concentrates. Scand. J. Metall. 31 (3), 221–228.
He, C.B., 1989. The measures to improve tungsten exchange capacity of 201 × 7 resin.
Int. J. Refract. Met. Hard Mater. 97, 33–35.
He, G.X., Zhao, Z.W., Wang, X.B., Li, J.T., Chen, X.Y., He, L.H., Liu, X.H., 2014. Leaching
kinetics of scheelite in hydrochloric acid solution containing hydrogen peroxide as
complexing agent. Hydrometallurgy 144–145, 140–147.
Huang, W.Z., Zhang, Q.X., Gong, B.F., Huang, S.Y., Luo, A.P., 1995. Production of pure
ammonium tungstate by one-step removal of P, As, Si, Mo through ion-exchange. Int.
J. Refract. Met. Hard Mater. 13 (4), 217–220.
Huggins, D.K., Queneau, P.B., Ziegler, R.C., Beckstead, L.W., Hogsett, R.F., 1982.
Separation of trace molybdenum from tungstate solutions. U.S. Patent 4,303,623.
ITIA, 2011. Primary uses of tungsten. International Tungsten Industry Association. http://
www.itia.info/tungsten-primary-uses.htmal (Accessed 12.12.2018).
Jiang, P.G., Xiao, Y.Y., Liu, W.J., Yu, X.B., 2019. Hydrogen reduction characteristics of
WO3 based on density functional theory. Results Phys. 12, 896–902.
Kahruman, C., Yusufoglu, I., 2006. Leaching kinetics of synthetic CaWO4 in HCl solutions
containing H3PO4 as chelating agent. Hydrometallurgy 81, 182–189.
Kalpakli, A.O., Ilhan, S., Kahruman, C., Yusufoglu, I., 2012a. Dissolution behavior of
calcium tungstate in oxalic acid solutions. Hydrometallurgy 121–124, 7–15.
Kalpakli, A.O., Arabaci, A., Kahruman, C., Yusufoglu, I., 2013. Int. J. Refract. Met. Hard
Mater. 37, 106–116.
Kalpakli, A.O., Ilhan, S., Kahruman, C., Yusufoglu, I., 2012b. Thermal decomposition
mechanism of ammonium phosphotungstate hydrate in air atmosphere. Int. J.
Refract. Met. Hard Mater. 31, 14–20.
Kalpakli, A.O., Yusufoglu, I., 2007. The investigation of the oxidation kinetics of phos-
photungsten suboxide. Metall. Mater. Trans. B 38 (2), 279–285.
Kholmogorov, A.G., Kononova, O.N., Kachin, S.V., 1999. Ion exchange hydrometallurgy
of tungsten using anion exchangers with long-chained cross-linking agents.
Hydrometallurgy 53, 177–187.
Kieffer, B.F., Baroch, E.F., 1981. Extractive Metallurgy of Refractory Metals, Proc. TMS-
AIME Annu. Meeting, pp. 273.
Lassner, S., 1995. From tungsten concentrates and scrap to highly pure ammonium
paratungstate (APT). Int. J. Refract. Met. Hard Mater. 13, 36–44.
13
Minerals Engineering 142 (2019) 105934
Lassner, E., Schubert, W.D., 1999. Tungsten: Properties, Chemistry, Technology of the
Element, Alloys and Chemical Compounds. Kluwer Academic/Plenum Publishers,
New York.
Leal-Ayala, D.R., Allwood, J.M., Petavratzi, E., Brown, T.J., Gunn, G., 2015. Mapping the
global flow of tungsten to identify key material efficiency and supply security op-
portunities. Resour. Conserv. Recy. 103, 19–28.
Li, X.B., Cui, Y.F., Zhou, Q.S., Li, J.P., Qi, T.G., Xu, S., Liu, G.H., Lin, G.R., Peng, Z.H., Li,
J.H., Xu, X.M., Shen, L.T., 2014a. A system for preparing APT from tungsten mineral
materials with multiple closed cycles. Chinese Patent 104263921 B.
Li, X.B., Cui, Y.F., Zhou, Q.S., Li, J.P., Qi, T.G., Xu, S., Liu, G.H., Lin, G.R., Peng, Z.H., Li,
J.H., Xu, X.M., Shen, L.T., 2014b. A system for preparing APT from tungsten mineral
materials with zero wastewater discharge. Chinese Patent 104263974 B.
Li, H.G., Liu, M.S., Sun, P.M., Li, Y.J., 1995. Caustic decomposition of scheelite and
scheelite-wolframite concentrates through mechanical activation. J. Cent. South
Univ. Technol. 2 (2), 16–20.
Li, K.C., Wang, C.Y., 1955. Tungsten. Reinhold Publishing Corporation, New York.
Li, X.B., Xu, X.M., Zhou, Q.S., Qi, T.G., Liu, G.H., Peng, Z.H., Cui, Y.F., Li, J.P., 2015.
Ca3WO6 prepared by roasting tungsten-containing materials and its leaching per-
formance. Int. J. Refract. Met. Hard Mater. 52, 151–158.
Li, X.B., Xu, X.M., Zhou, Q.S., Qi, T.G., Liu, G.H., Peng, Z.H., Cui, Y.F., Li, J.P., 2016.
Ca3−x(Fe, Mn)xWO6 (0 < x ≤ 1) prepared from tungsten-containing materials and its
leachability in aqueous ammonium carbonate solution. Int. J. Refract. Met. Hard
Mater. 57, 93–100.
Li, X.B., Shen, L.T., Zhou, Q.S., Peng, Z.H., Liu, G.H., Qi, T.G., 2017. Scheelite conversion
in sulfuric acid together with tungsten extraction by ammonium carbonate solution.
Hydrometallurgy 171, 106–115.
Li, J.T., Zhao, Z.W., 2016. Kinetics of scheelite concentrate digestion with sulfuric acid in
the presence of phosphoric acid. Hydrometallurgy 163, 55–60.
Liu, Y.J., Ma, D.S., 1987. Geochemistry of Tungsten. Science Press, Beijing (In Chinese).
Ma, X.T., Qi, C.C., Ye, L.P., Yang, D.L., Hong, J.L., 2017. Life cycle assessment of tungsten
carbide powder production: A case study in China. J. Clean. Prod. 149, 936–944.
Martins, J.P., 1996. Kinetics of soda ash leaching of low-grade scheelite concentrates.
Hydrometallurgy 42 (2), 221–236.
Martins, J.I., 2003. Leaching of synthetic scheelite by nitric acid without the formation of
tungstic acid. Ind. Eng. Chem. Res. 42, 5031–5036.
Martins, J.I., 2014. Leaching systems of wolframite and scheelite: a thermodynamic ap-
proach. Mineral Process Extr. Metall. Rev. 35, 23–43.
Martins, J.P., Martins, F., 1997. Soda ash leaching of scheelite concentrates: the effect of
high concentration of sodium carbonate. Hydrometallurgy 46 (1–2), 191–203.
Martins, J.I., Moreira, A., Costa, S.C., 2003. Leaching of synthetic scheelite by hydro-
chloric acid without the formation of tungstic acid. Hydrometallurgy 70, 131–141.
Maslenitsky, I.N., 1939. The autoclave-soda process for the treatment of tungsten con-
centrate. Tsvetnye Metall. 4–5, 140–143.
Meerson, G.A., Khavskii, N.N., 1961. Hydrometallurgic heterogeneous reaction happened
during the grinding. Izv. Akad. Nauk SSSR, Otd. Tekh. Nauk Metall. Topl. 5, 36–42.
Moris, M.A., Diev, F.V., Coca, J., 1999. Solvent extraction of molybdenum and tungsten
by Alamine 336 and DEHPA in a rotating disc contactor. Sep. Purif. Technol. 17,
173–179.
Pastukhov, A.M., Skripchenko, S.Y., 2015. Process for recovering molybdenum and
tungsten from MoS3/WS3 precipitates. Hydrometallurgy 157, 78–81.
Paulino, J.F., Afonso, J.C., Mantovano, J.L., Vianna, C.A., Cunha, J.W.S.D., 2012.
Recovery of tungsten by liquid–liquid extraction from a wolframite concentrate after
fusion with sodium hydroxide. Hydrometallurgy 127, 121–124.
Potashnikov, Y.M., Gamol'skii, A.M., Mokhosoev, M.V., Kozlova, F.M., 1970. Kinetics of
the dissolution of calcium tungstate in oxalate acid solution. Zh. Neorg. Khim 15 (2),
502–508.
Qian, J.X., 1964. Tungsten Metallurgy. China Industry Press, Beijing (In Chinese).
Quatrini, L.R., Martin, B.E., 1982. Tungsten recovery from tungsten ore concentrates by
caustic digestion: U.S. Patent 4,353,879.
Quatrini, L.R., Terlizzi, M.B., Martin, B.E., 1982a. Tungsten recovery from tungsten ore
concentrates by caustic digestion. U.S. Patent 4,353,878.
Quatrini, L.R., Vogt, M.C., Martin, B.E., 1982b. Tungsten recovery from tungsten ore
concentrates by caustic digestion: U.S. Patent 4,353,881.
Quatrini, L.R., 1982. Tungsten recovery from tungsten ore concentrates by caustic di-
gestion: U.S. Patent 4,353,880.
Razavizadeh, H., Ershad, L.A., 2006. Production of tungsten via leaching of scheelite with
sulfuric acid. Miner. Metall. Process. 23 (2), 67–72.
Reck, B.K., Graedel, T.E., 2012. Challenges in metal recycling. Science 337, 690–695.
Rudnick, R.L., Gao, S., 2003. Composition of the continental crust. Treatise Geochem. 3,
659.
Schubert, W.D., Zeiler, B., 2014. Recycling of tungsten: technology, potential and limits.
In: Proceedings of the ITIA 27th Annual General Meeting, Toronto.
Shemi, A., Magumise, A., Ndlovu, S., Sacks, N., 2018. Recycling of tungsten carbide scrap
metal: A review of recycling methods and future prospects. Miner. Eng. 122,
195–205.
Shen, L.T., Li, X.B., Taskinen, P., 2018a. Thermodynamics of tungsten ores decomposition
process options. Extraction 2018, The Minerals, Metals & Materials Series, https://
doi.org/10.1007/978-3-319-95022-8_206.
Shen, L.T., Li, X.B., Zhou, Q.S., Peng, Z.H., Liu, G.H., Qi, T.G., Taskinen, P., 2018b.
Kinetics of scheelite conversion in sulfuric acid. JOM 70, 2499–2504.
Shen, L.T., Li, X.B., Zhou, Q.S., Peng, Z.H., Liu, G.H., Qi, T.G., Taskinen, P., 2018c.
Wolframite conversion in treating a mixed wolframite-scheelite concentrate by sul-
furic acid. JOM 70, 161–167.
Shen, L.T., Li, X.B., Zhou, Q.S., Peng, Z.H., Liu, G.H., Qi, T.G., Taskinen, P., 2018d.
Sustainable and efficient leaching of tungsten in ammoniacal ammonium carbonate
solution from the sulfuric acid converted product of scheelite. J. Clean. Prod. 197,
L. Shen, et al.
690–698.
Song, Y.Q., Tsuchida, Y., Matsumiya, M., Uchino, Y., Yanagi, I., 2018. Separation of
tungsten and cobalt from WC-Co hard metal wastes using ion-exchange and solvent
extraction with ionic liquid. Miner. Eng. 128, 224–229.
Srinivas, K., Sreenivas, T., Natarajan, R., Padmanabhan, N.P.H., 2000. Studies on the
recovery of tungsten from a composite wolframite–scheelite concentrate.
Hydrometallurgy 58 (1), 43–50.
Srivastava, R.R., Lee, J.C., Bae, M., Kumar, V., 2019. Reclamation of tungsten from car-
bide scraps and spent materials. J. Mater. Sci. 54, 83–107.
Sun, P.M., Li, H.G., Li, Y.J., Zhao, Z.W., Huo, G.S., Sun, Z.M., Liu, M.S., 2003.
Decomposing scheelite and scheelite-wolframite mixed concentrate by caustic soda
digestion. J. Cent. South Univ. Technol. 10 (4), 297–300.
Tkaczyk, A.H., Bartl, A., Amato, A., Lapkovskis, V., Petranikova, M., 2018. Sustainability
evaluation of essential critical raw materials: cobalt, niobium, tungsten and rare earth
elements. J. Phys. D: Appl. Phys. 51 203001(26pp).
Trasorras, J.R.L., Wolfe, T.A., Knabl, W., Venezia, C., Lemus, R., Lassner, E., Schubert,
W.D., Lüderitz, E., Wolf, H., 2016. Tungsten, tungsten alloys, and tungsten com-
pounds. Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH Verlag GmbH &
Co. KGa A, Weinheim.
Trent, E.M., 1946. Process of separating hard constituents from sintered hard metals. US
Patent No. 2,407,752.
USGS, 2009. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2009.
USGS, 2010. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2010.
USGS, 2011. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2011.
USGS, 2012. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2012.
USGS, 2013. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2013.
USGS, 2014a. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2014.
USGS, 2014b. Conflict minerals from the democratic republic of the congo: Global
tungsten processing plants, a critical part of the tungsten supply chain. Version 1.1,
August 2014.
USGS, 2015. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2015.
USGS, 2016. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2016.
USGS, 2017. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2017.
USGS, 2018. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, January
2018.
USGS, 2019. Tungsten, U.S. Geological Survey, Mineral Commodity Summaries, February
2019.
Vezina, J.A., Gaw. W.A., Lalibert, J.J., 1970. Continuous recovery of tungstic trioxide.
European Patent, 836441.
Wan, L.S., Zhao, L.F., Li, H.C., 2012. The advance and development of APT’s environment
friendly smelting technology in Zhangyuan Tungsten Co., Ltd. China Tungsten Ind.
14
Minerals Engineering 142 (2019) 105934
27(1), 47-49. (in Chinese).
Wan, L.S., Huang, X.J., Deng, D.F., Li, H.C., Chen, Y.M., 2015b. Synthesis of scheelite
from sodium tungstate solution by calcium hydroxide addition. Hydrometallurgy
154, 17–19.
Wan, L.S., Yang, L., Chen, Y.M., Zhao, L.F., Li, H.C., 2015a. Synthesis of scheelite with
wolframite and calcium carbonate by a direct solid-state synthesis route. Int. J.
Refract. Met. Hard Mater. 48, 301–304.
Wigginton, N., Yeston, J., Malakoff, D., 2012. More treasure than trash. Science 337,
662–663.
Wu, Y.J., Dang, J., Lv, Z.P., Zhang, R., 2018. The preparation of tungsten carbides and
tungsten powders by reaction of tungsten trioxide with methanol. Int. J. Refract. Met.
Hard Mater. 76, 99–107.
Wu, X.S., Zhang, G.Q., Zeng, L., Zhou, Q., Li, Z.H., Zhang, D., Cao, Z.Y., Guan, W.J., Li,
Q.G., Xiao, L.S., 2019. Study on removal of molybdenum from ammonium tungstate
solutions using solvent extraction with quaternary ammonium salt extractant.
Hydrometallurgy 186, 218–225.
Xu, X.M., Zhou, K.C., Li, X.B., Zhou, Q.S., Qi, T.G., Liu, G.H., Peng, Z.H., 2019. Leaching
of synthetic Ca3WO6 with ammoniacal ammonium carbonate solution under atmo-
spheric pressure: A fundamental study. Hydrometallurgy 184, 55–66.
Xuin, G.H., Yu, D.Y., Su, Y.F., 1986. Leaching of scheelite by hydrochloric acid in the
presence of phosphate. Hydrometallurgy 16, 27–40.
Yang, J.H., He, L.H., Liu, X.H., Ding, W.T., Song, Y.F., Zhao, Z.W., 2018. Comparative
kinetic analysis of conventional and ultrasound-assisted leaching of scheelite by so-
dium carbonate. Trans. Nonferrous Met. Soc. China 28 (4), 775–782.
Yang, Y., Xie, B.Y., Wang, R.X., Xu, S.M., Wang, J.L., Xu, Z.H., 2016. Extraction and
separation of tungsten from acidic high-phosporus solution. Hydrometallurgy 164,
97–102.
Yih, S.W.H., Wang, C.T., 1979. Tungsten: Sources, Metallurgy, Properties, and
Applications. Plenum Press.
Zeiler, B., Schubert, W.D., Bartl, A., 2018. Recycling of Tungsten: Current share, economic
limitations and future potential. ITIA Tungsten Newsletter, May 2018.
Zhang, G.Q., Guan, W.J., Xiao, L.S., Zhang, Q.X., 2016. A novel process for tungsten
hydrometallurgy based on direct solvent extraction in alkaline medium.
Hydrometallurgy 165, 233–237.
Zhang, L.W., Nie, Z.R., Xi, X.L., Ma, L.W., 2018. Electrochemical separation and extrac-
tion of cobalt and tungsten from cemented scrap. Sep. Purif. Technol. 195, 244–252.
Zhang, Q.X., Zhao, Q.S., 2005. Metallurgy of Molybdenum and Tungsten. Press of
Metallurgical Industry, Beijing (In Chinese).
Zhao, Z.W., Li, J.T., 2013. Meyhod for extracting tungsten from scheelite. US Patent
20130195737A1.
Zhao, Z.W., Hu, F., Hu, Y.J., Wang, S.B., Sun, P.M., Huo, G.S., Li, H.G., 2010. Adsorption
behaviour of WO42− onto 201× 7 resin in highly concentrated tungstate solutions.
Int. J. Refract. Met. Hard Mater. 28 (5), 633–637.
Zhao, Z.W., Liang, Y., Li, H.G., 2011b. Kinetics of sodium hydroxide leaching of scheelite.
Int. J. Refract. Met. Hard Mater. 29, 289–292.
Zhao, Z.W., Li, J.T., Wang, S.B., Li, H.G., Liu, M.S., Sun, P.M., Li, Y.J., 2011a. Extracting
tungsten from scheelite concentrate with caustic soda by autoclaving process.
Hydrometallurgy 108 (1–2), 152–156.
Zhao, Z.W., Liang, Y., Liu, X.H., Chen, A.L., Li, H.G., 2011c. Sodium hydroxide digestion
of scheelite by reactive extrusion. Int. J. Refract. Met. Hard Mater. 29, 739–742.