Naomie Kad Final Thesis

本科毕业设计(论文)
GRADUATION DESIGN(THESIS)
废旧硬质合金阳极溶出钝化
题目：
现象的研究
学生姓名：奥美
指导教师：赵中伟孙丰龙
学院：冶金与环境
专业班级： 1804 班
本科生院制
2022 年 6 月
废旧硬质合金阳极溶出钝化现象的研究
摘要
钨是重要的战略性稀有金属，全球资源储量估计约为 700 万吨，而中国作为主要
生产国，年产量约 73000 吨。然而，目前钨二次资源的回收却并不理想。以钨做主要
的产品硬质合金为例，目前中国的回收率不足 30%，同时硬质合金中的钴也难以回收
利用。回收硬质合金的主要方法有锌熔法、氧化法、电化学溶出法。其中电化学溶出
过程简单，可直接获得再生碳化钨粉末，因此受到研究者的关注。电化学溶出是将硬
质合金作为阳极，在溶液中使粘结相（如钴）被氧化以离子的形式进入溶液中。但该
方法由于过程中形成一层 WC，产生阳极钝化，从而影响该方法的效率。因此本文对
阳极钝机理和实验条件进行了深入的研究。本文中，我们提出了电化学工艺对硬质合
金废料进行阳极钝化和溶解的想法。我们使用包含阴极和阳极的电站进行了设置，阳
极分别连接盐酸（HCl）和硫酸（H2SO4）溶液中的硬质合金废料，并使用不同恒定电
压的阳极电流变化从（0.5-1.25V）进行研究，以及分析了电压变化与不同的恒定电流
从（0.05-0.2 A）。本文具体结论如下：
1. 当时间从（30-1440mins）增加时，盐酸（HCl）和硫酸（H2SO4）同时在此情
况下，在（0.5V-1.25V）范围内的各种恒定电压下，研究电流随时间的变化情况。
2. 两种解决方案均在 1V 的恒定电压下实现了高水平的阳极电流变化。当恒定
电压 1 V 下比较两种溶液阳极电流变化时，HCl 仍然证明对废钢电解过程比 H2SO4 有
效。0.1M HCl 中 0.05 恒定电流下废钢的电压随时间在第一个 2 到 5 个小时急剧增加
(1.59 V-1.80 V)。
3. 当废料在 0.1M H2SO4 溶液中以电流密度时，即使在没有盐酸 (HCl) 的情况
下，电压在前 6-8 小时内从 1.6-1.7 V 增加，并在接下来的 24 小时内逐渐增加。
4. 当两种废料分别在 0.4M HCl 和 H2SO4 溶液中电解时，电压也会升高。硫
酸 (H2SO4) 为 0.2 的废品钝化的机会低于盐酸 (HCl) 为 0.2 的废品。表面组分在转变
为 WC 后暴露于不溶性钨酸矿物中，钨酸矿物是阳极钝化的结果。
基于此分析，这些发现为阳极钝化和硬质合金废料的溶解提供了合适的方法。
30 图，7 表，102 篇参考文献
关键词：硬质合金，电化学溶解，阳极钝化，回收
I
Research of anodic passivation in the process of electrochemical dissolution for

cemented carbide scrap
Abstract
Tungsten is an important strategic rare metal with an estimated global resource reserve of
about 7 million tons, while China, as a major producer, has an annual output of about 73,000
tons. However, the current recovery of tungsten secondary resources is not ideal. Taking
tungsten as the main product cemented carbide as an example, the current recovery rate in
China is less than 30%, and the cobalt in cemented carbide is also difficult to recycle. The
main methods of recycling cemented carbide are zinc melting method, oxidation method and
electrochemical stripping method. Among them, the electrochemical dissolution process is
simple, and the regenerated tungsten carbide powder can be directly obtained, so it has
attracted the attention of researchers. Electrochemical dissolution is to use cemented carbide
as an anode in solution, so that the binder phase (such as cobalt) is oxidized into the solution
in the form of ions. However, in this method, since a layer of WC is formed during the
process, anode passivation occurs, thereby affecting the efficiency of the method. Therefore,
the anode passivation mechanism and experimental conditions are deeply studied in this
paper.
In this paper, we proposed the idea of electrochemical process for anodic passivation and
dissolution for cemented carbide scrap. We conducted a set-up using the power station that
contains both cathode and anode with the anode connected to the cemented carbide scrap in
hydrochloric acid (HCl) and sulfuric acid (H 2SO4) solution separately, and investigated the
anodic current variation utilizing different constant voltage from (0.5-1.25V), and also
analyzing voltage variation with different constant current from (0.05-0.2A). The specific
conclusion are as follows:
1. When the time increases from (30-1440mins), there was a decrease in the variation
of anodic current at various constant voltages ranging from (0.5V-1.25V) in the presence of
both hydrochloric acid (HCl) and sulfuric acid (H2SO4) solutions.
2. The high level of anodic current variation was achieved at the constant voltage of
1V for both solutions. When both solution anodic current variation was compare at the
constant voltage of 1, HCl still prove to be efficient for the scrap electrolysis process than
H2SO4.Voltage with time for the scrap at 0.05 constant current in 0.1M HCl increase steeply
in the first 2-5 h from (1.59 V-1.80 V).
II
3. When the scrap was electrolyzed at 0.5 in 0.1M H 2SO4 solution, even in the absence
of hydrochloric acid (HCl), the voltage increases in the first 6-8 h from 1.6-1.7 V and
gradually over the next 24 h.
4. When both scraps electrolyzed in 0.4M of HCl and H2SO4 solution separately, the
voltage also increases. The scrap at 0.2 for sulfuric acid (H2SO4) had a lower chance for
passivation than the scrap at 0.2 for hydrochloric acid (HCl). The surface components were
exposed to insoluble tungsite acid mineral after being transitioned to WC, and the tungsite
acid mineral was the result of anodic passivation.
Based on this analysis, these findings provide a suitable method for anodic passivation
and the dissolution of cemented carbide scrap.
32 Figures，9 Tables， and 102 References
Keywords: Cemented carbide, Electrochemical dissolution, anodic passivation, recycling
III
ACRONYMS
ACRONYMS TERMINOLOGY
AP Anodic passivation
As Arsenic
BGS British Geological Survey
CC Constant Current
CP Chronopotentiometry
CRMs Critical Raw Materials
CV Constant Voltage
EC Electrochemical
EC European Commission
ED Electro-dissolution
GHG greenhouse gas
H2SO4 Sulfuric Acid
HCl Hydrochloric acid
PP Potentiodynamic polarization
EE Earth Elements
SDG Sustainable Development Goals
WC tungsten carbide
Wc-Co tungsten carbide cobalt
IV
Table of content
CHAPTER 1: LITERATURE REVIEW....................................................................................

1.1 GENERAL OVERVIEW........................................................................................................
1.1.1 Critical raw materials.................................................................................................
1.1.2 Tungsten.....................................................................................................................
1.1.3 Cobalt.......................................................................................................................11
1.1.4 Tungsten Carbide.....................................................................................................14
1.1.5 Anodic passivation...................................................................................................20
1.2 ELECTROCHEMICAL PROCESS..........................................................................................21
1.2.1 Principles of electrochemical process......................................................................21
1.2.2 W and Co recovery through EC process..................................................................22
1.2.3 Potentiodynamic polarization..................................................................................22
1.2.4 Chrono-potentiometric.............................................................................................23
1.2.5 Chrono-amperometric..............................................................................................24
1.3 RESEARCH SIGNIFICANCE, CONTENT, INNOVATION POINT AND TECHNICAL ROUTE......24
1.3.1 Research significance...............................................................................................24
1.3.2 Research content......................................................................................................24
1.3.3 Innovation point.......................................................................................................25
1.3.4 Technical route.........................................................................................................25
CHAPTER 2: MATERIALS AND METHODS......................................................................26
2.1 EXPERIMENTAL MATERIALS AND METHODS....................................................................26
2.1.1 Experimental materials............................................................................................26
2.1.2 Cobalt scrab dissolution preparation (Set-up)..........................................................26
2.1.3 Preparation of HCl and H2SO4.................................................................................27
2.1.4 Experimental design.................................................................................................27
2.1.5 Constant voltage experimental procedure using (HCl and H2SO4)..........................28
2.1.6 Constant current experimental procedure using (HCl and H2SO4)..........................28
2.2 TUNGSTEN COBALT SCRAP CHARACTERIZATION............................................................29
CHAPTER 3: CURRENT VARIATION OF COBALT SCRAP ANALYSIS AT
DIFFERENT CONSTANT VOLTAGES (CV).......................................................................30
3.1 INTRODUCTION................................................................................................................30
3.2 RESULTS AND DISCUSSION..............................................................................................30
V
3.2.1 Constant Voltage analysis........................................................................................30

3.3 SUMMARY........................................................................................................................34
CHAPTER 4: VOLTAGE VARIATION OF COBALT SCRAP ANALYSIS AT
DIFFERENT CONSTANT CURRENT (CC)..........................................................................35
4.1 INTRODUCTION................................................................................................................35
4.2 RESULTS AND DISCUSSION..............................................................................................35
4.2.1 Constant Current analysis........................................................................................35
4.3 SUMMARY........................................................................................................................40
CHAPTER 5: CONCLUSION AND RECOMMENDATION................................................42
5.1 CONCLUSION...................................................................................................................42
5.2 RECOMMENDATION.........................................................................................................42
REFERENCES.........................................................................................................................44
ACKNOWLEDGEMENT........................................................................................................51
VI
CHAPTER 1: LITERATURE REVIEW
1.1 General Overview

Society today is heavily dependent upon technology, the advancement of which is highly
reliant with an ever variety of raw materials. Because the advantages of technologies are
influenced by raw material supply, their potential consequences have become extremely
important for European industry, resulting in the emergence of numerous policy measures and
research programs to address the growing concerns about the future and security of raw
material supply. The emphasis on critical metals stems from a number of to provide features,
such as integrated supply chains, similar manufacturing processes, and the ability to recycle
end-of-life products. Nevertheless, there are many other raw materials (non-critical and/or
non-metallic) with the same significance and supply risks [1].
The supply of critical raw materials (CRMs) can come from either principal (the mining
industry) or secondary information (through recycling methods). Because Europe needs to
import the majority of the raw materials required by European industries, its safety is largely
dependent on effective resources planning all through the lifecycle and a dedication to
recycling CRMs from secondary resources. Towards that large extend, replacement and
reprocessing are regarded as risk-reduction measures for developing the EU CRM list .
[2]
Tungsten (W) and cobalt (Co) are two of these CRMs that have been recognized as being
critical to EU industries since 2011. Tungsten and Co are two CRMs that have higher
recyclability (42 % for W and 35 % for Co). Because of their commercial significance and the
risk of supply shortage, they managed to remain on this list in 2014, 2017, and 2020 .
[2, 3]
Tungsten is a steady transition metal with numerous applications including cemented

carbides, mill products, alloys, and steels, whereas cobalt is a ferromagnetic metal used
primarily in high - temperature and electrostatic alloys .Cemented carbide, which accounts
[4]
for the vast majority of tungsten global demand, comprised of a carbide cutting tool made of
fine particles of W and Co (the binder which holds tungsten carbide together), with a large
variety of differences in carbide particle sizes and carbide: binder/binder ratio [1].
Because of its excellent wear resistance, mechanical hardness, and toughness, cobalt is a
phenomenal binding metal that is commonly used to manufacture metalworking tools .
[5]
According to the global market distribution of cutting tools in 2018 by cutting technique and
work material, milling, turning, and drilling are the most commonly used procedures in
principal machining operations (almost 87 % of the total tooling market) . Tungsten carbide
[6]
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(WC-Co) scraps have long been regarded as a valuable secondary information of W and Co
metals. Reprocessing these carbides necessitates different methods such as hydrometallurgical
or pyrometallurgical leaching or reduction by hydrogen to produce W powder, or even direct
leaching of WC scrap in concentrated acid/alkali solutions. When compared to other recycling
methods, electrochemical technologies have developed as an appealing method for recycling
WC-Co waste because it is a single-step dissociation process that utilizes very little energy
and produces very pure results . In terms electrolytes type used, anode passivation during
[7]
anodic dissolution is a major concern, as it can reduce the process's effectiveness, limiting
electro dissolution. As a result, making improvements on anodic dissolution is regarded as
one of the most difficult steps in the electrochemical reprocessing of WC waste in terms of
productivity . Instead of anodic dissolution, the current study used restore W and Co from
[8]
WC-Co scrap powder produced by cutting tools. An electric field induces ED, which is one of
the most possessing methods for separating ionic compounds from an aqueous solution or
other uncharged matrices .The ED process is used to remove the impurities from solid
[9]
matrices, and it has been demonstrated to be successful in eliminating heavy metals from solid
matrices, with discharge rates exceeding 80% and reduced energy consumption [10].
1.1.1 Critical raw materials
The European Green Agreement is the innovative EU growth of the economy strategy
adopted by the European Commission (EC) in 2019, as part of actions associated with the
implementation of the United Nations' 2030 Agenda and Sustainable Development Goals
(SDG). As the EU revealed in 2014, one of the most essential aspects of this plan is to
mobilize industry for a clean and circular economy model. The reuse envisions a shift from a
linear to a circular model in which waste can be transformed into a valuable resource. As a
result, it is suggested that raw materials be used more efficiently and that recycling be
improved [11]
. Raw materials are essential in the manufacture of a wide range of goods and
tools used in daily life. Because the EU industry is heavily reliant on imports for so many raw
materials, the EU is highly vulnerable at all stages of the production process in various
sectors. They are an essential component of the EU's growth and competitiveness, and their
importance will grow in tandem with the replacement of fossil fuels. Critical raw materials
(CRMs) are those that have the greatest economic importance and a high supply risk [12, 13].
CRMs demand is expected to double between 2010 and 2030 due to the speed of
technological developments and the fast growth of developing markets. The Green Deal's
climate ambition strengthens the link to CRMs, because achieving zero net emissions of
greenhouse gases by 2050 will necessitate electrification efforts and expansion of energy
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supply sources, which will necessitate a significant rise in raw materials . For these reasons,
[14]
the European Commission launched an integrative approach called the European Raw
Materials Initiative in 2008. Its goals are to manage the increasing concern about security and
to improve access to raw materials for the Eu market. One of the Project's most significant
actions was the compilation of a list of CRMs at the EU level [15, 16] . This EU-level evaluation,
which began in 2011, discusses a variety of raw materials and is revised every three years.
The EU's fourth and the most recent CRMs list was accepted in 2020, and it contains 30
CRMs, as shown in Table 1-1. Even when the raw material is not deemed essential, its
accessibility and significance to the EU economy should not be overlooked. Furthermore, the
range of available data and potential changes in EU and global markets may have an impact
on the list in the future [17]
. The US Geological Research study has a similar list, which was
updated in 2018 in the Completed List of Critical Minerals (Table 1-2). These "critical
minerals" have a defenseless supply chain and a vital function in the production or
manufacture, and their exclusion would have a number of economic and national security
implications [18]. Even though the majority of critical minerals for the US Geological research
(Table 1-2) are the same as those for the European Commission (Table 1-1), a few differences
can be found and are showcased in both tables. This is due to the various economies,
factories, or mineral wealth. There are some other technical term or mixture differences
between the two lists, such as barite/baryte (US and EN English) or Rare Earth Elements
Group on the US list, which relates to Heavy REE and Light REE on the EU list.
Table 1-1 List of Critical Raw Materials for the EU in 2020. Materials that are not present in the US
Geological Survey list are bolded
2020 Critical Raw materials
Antimony Germanium Platinum Group Metals

Baryte Hafnium Phosphate rock
Bauxite Heavy Rare Earth Elements Phosphorus
Beryllium Indium Scandium
Bismuth Light Rare Earth Elements Silicon Metal
Borate Lithium Strontium
Cobalt Magnesium Tantalum
Coking Coal Natural Graphite Titanium
Fluorspar Natural Rubber Tungsten
Gallium Niobium Vanadium
第 3 页/共 51 页
Table 1-2. Final List of Critical Minerals for US Geological Survey. Materials that are not present in the
EU CRMs list are bolded
Final list of Critical Minerals 2018
Aluminium (bauxite) Graphite (natural) Rubidium
Antimony Hafnium Scandium
Arsenic Helium Strontium
Barite Indium Tantalum
Beryllium Lithium Tellurium
Bismuth Magnesium Tin
Cesium Manganese Titanium
Chromium Niobium Tungsten
Cobalt Platinum Group Metals Uranium
Fluorspar Potash Vanadium
Gallium Rare Earth Elements Group Zirconium
Germanium Rhenium
China is the EU's primary supplier of CRMs, but many other countries, including the
United States (beryllium), Turkey (borate), Chile (lithium), and South Africa, have major
share of the EU supply for specialized CRMs (platinum group metals). The EU also depends
heavily on single EU companies for hafnium and strontium supplies [19].Some distinctions
between the 2018 and 2020 findings on the EU's CRMs necessities can illustrate why the EU
has to always monitor its actual supply to have a more realistic view of the European raw
material supply assessed.
Presently, the removal and processing of raw materials is currently responsible for
roughly half of total greenhouse gas (GHG) emissions and much more than 90% of habitat
loss and osmotic stress. Because reprocessing accounts for only 12% of the materials used in
the European economy, rising collection and recycling rates is a primary concern [20]
. Despite
the fact that several CRMs have a high technical and real economic recycling possibility, and
despite state subsidies to adopt a recycling industry, the recycling input rate of CRMs is
typically low due to a variety of factors: Many CRM selection and recycling techniques are
not yet competitively priced; the supply of several CRMs is presently locked up in longlife
assets, implying slowdowns between production and scrapping and having a negative impact
on existing recycling input rates; demand for many CRMs is increasing across several sectors
faster than recycling can meet that demand [20].
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1.1.1.1 The importance of raw materials

The growing challenge of obtaining direct connections to metals and minerals required
for economic manufacturing has gained extensive attention from the general public, economic
actors, and politicians over the last decade. Raw materials are required not only for the
manufacture of a wide variety of goods and services used in daily life, but also for the
development of the developing innovations, which are especially important for more eco-
efficient technologies and internationally competitive products [21].
The importance of critical raw materials are as follows:
1. Industrial value chains - non-energy raw materials are connected to all industry
sectors at all stages of supply chain.
2. Strategic technologies - Connectivity to a rising number of raw materials is critical
to technological advancement and life quality. A mobile phone, for instance, may contain up
to 50 different types of metals, all of which make a contribution to its small size, light in
weight, and capabilities.
3. Climate, energy and environment - Raw materials are intrinsically tied to cleaner
production, which are required to achieve carbon impartiality objectives by 2050. They are
indispensable in solar panels, wind turbines, electric vehicles, and energy-saving lighting [22].
In Europe, the industrial base (the producer of finished goods and implementations) and
the refineries sector (metallurgy, for example) are frequently regarded as more essential than
the extractive industry (e.g. mining activities). Furthermore, the European industry does not
cover the entire value chain of raw materials, with a significant imbalance between both the
upstream (extraction / harvesting) and downstream steps (manufacturing and use).
Nonetheless, the need for primary materials, such as ores and concentrates, as well as highly
processed materials, is critical for the wealth - and even survival - of European industries, as
well as the jobs and economic system that they support [23]. In reality, so little non-energy raw
material extraction occurs inside of European Member
States, with the vast bulk of ore and focuses, refined components, or metals originating
in non-European countries. The graph below depicts the major global manufacturers of all
candidate critical raw materials (in terms of number of raw materials, not in terms of tonnage)
(Fig. 1-1). China clearly dominates, with China extracting 59 percent of the raw materials
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assessed 26. South Africa and the United States are also the primary producers of the raw
materials under consideration.
Figure 1-1: The primary global suppliers of all candidate critical raw materials evaluated (based on the
number of raw materials supplied on an annual basis and percentage base on the number of raw material
supply.
1.1.1.2 The challenge of critical raw materials
The vibrant changes in technology and rapid growth of emerging economies have
resulted in increasing, albeit volatile, request for a variety of metals and minerals. Trying to
secure a constant supply of such critical raw materials has become a big challenge for national
and regional economic systems with restricted indigenous environmental assets, such as the
EU economy, which is heavily dependent on imported supplies of many minerals and metals
required by industry. Most of these components are presently obtained in only a few
countries, with China becoming the major provider and also consumer of several main raw
materials, such as antimony, bismuth, magnesium, REEs, and so on. This raises the possibility
of supply problems and supply weakness throughout the value chain. The probability of
supply chain disruption is increased more by the fact that many metals' production process,
smelting, and refining are also focused in a limited number of countries. In addition to high
concentration, some major producers strictly control and limit the export of raw materials,
intermediate products, and/or metals in order to protect them for their domestic industries, by
第 6 页/共 51 页
trying to impose a variety of export limitation measures that are frequently regarded as
distortive to free markets.
In recent time, the European Commission initiated the European Raw Materials Initiative
to address the increasing worries about safeguarding valuable raw materials for the EU
economy. It is a comprehensive strategy that establishes aimed measures to safeguard and
enhance raw material access[24]. These strategies are as follows:
➢ Equitable and efficient raw material supply from global markets;
➢ Promoting long-term production within the EU; and
➢ Increasing resource productivity and encouraging recycling
For the successful execution of EU raw materials policies, it is important to understand
the vital raw materials for the European economy, their stocks and tends to flow, as well as
the industry, and to recognize shortfalls. One of the European Raw Materials Proposal's action
plans was to compile a list of crucial non-energy raw materials (CRMs) at the EU level.
1.1.2 Tungsten
1.1.2.1 General properties
Tungsten, also recognized as wolfram (chemical symbol W), is a solid and rare
transformation metalloid with a greyish-white lustrous look in Periodic Table Group VI.
Tungsten is mainly found in primary mineral such as scheelite (CaWO4), which comprise
between 0.1 and 5% WO3 [25, 26]
. Tungsten is indeed a CRM with numerous applications,
being the most important in the manufacturing of cemented carbides, accompanied by mill
products, alloys, and steels [27]
. Tungsten has the second highest melting point of any element
(3420 °C), only exceeded by carbon (3550 °C). It also has the minimum vapor pressure, the
lowest compressibility, an extremely high density (19.3 g/cm 3), a high elasticity modulus, low
thermal expansion, and good thermal conductivity of any metal. Pure tungsten has a body-
centered-cubic structure that is physically weak at room temperature but becomes ductile at
higher temperatures(100-500 °C) .Tungsten has some unusual properties, which are
[1, 7]
summarized in Table 1-3.

In general, magmatic-hydrothermal processes combined with granitic intrusions form W
deposits. These deposits can be discovered on the intrusive's periphery (greisen, porphyry,
stockwork, and vein deposits) as well as in its exterior (stockwork, vein, and skarn deposits).
Tungsten deposits are frequently associated with molybdenum or tin mineralization
[28]
.However, the commercial production mined main tungsten-bearing ores, scheelite and
wolframite, are now becoming increasingly scarce [26].Furthermore, due to the waste rock that
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must be removed in order to access the ore, W mines produce so much waste than was
initially mined. The concentration of byproducts in open pit mines causes significant
landscape and other environmental issues [29]
.Because of the aforementioned reasons, the EU
and the US acknowledged W as one of the 30 CRMs [30]
,as well as one of the 35 critical
mineral commodities [31].
Tungsten Properties
Atomic Number 74 Atomic Mass 183.86 u
14 4 2
Electron Distribution [Xe]4f 5d 6s Oxidation Number -2, -1, 0, +1, +2, +3, +4, +5
Melting Point 3420 ͦ C Boiling Point 5530 ͦ C
Electronegativity 2.36 Isotope 180, 182, 183, 184, 186
Density 19.3 g/cm3 Atomic Volume 9.53 cm3/mol
Ionization Energy 770kJ/mol
Table 1-3. General properties of tungsten (W) adapted from Midwest Tungsten Service
1.1.2.2 Chemistry of Tungsten

Tungsten has a complicated evolution of species with many valence states ranging from -
2 to +6, with +6 being the most common. Tungsten is usually found in the environment as the
oxyanion tungstate WO42-, which can crystallize with itself and other ions to produce a variety
of W structures [7]
. W interaction with aqueous solutions seems to be quite complicated,
resulting in a series of chemical reactions that are difficult to control and identify. However,
W's low corrosion rate can be used to its benefit as an anode in an electrochemical cell to
prevent hydrocarbons release [32]
. Tungsten is an immobile metal that is resilient to many
elements and compounds, including molten metals, and seems to be constant to mineral acids
in cooler conditions while being fractionally attacked at higher temperatures. The reaction of
W in aqueous systems of mineral acids and alkalis is shown in Table 1-4, illustrating that the
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large percentage do not attack W. The existence of oxidizing agents in mixture with acids or
alkalis, on the other hand, can lead to rapid dissolution.
Table 1-4 Reaction of tungsten metal with acids and alkalis

Reagent Temperature
20 ͦ C 100-110 ͦ C
HF None None
HNO3 Slight attack Oxidation
H2SO4 None Slight attack
HCl None Slight attack
H3PO4 None Slight attack
H2O2 None Dissolution
NH4OH None None
KOH None None
NaOH None None
HCl + HNO3 Oxidation Dissolution
HF + HNO3 Dissolution Dissolution
KOH + H2O2 Slight attack Dissolution
Table 1-4 also mentions essential acid combinations for tungsten dissolution. Because W
is easily attacked at room temperature, a combination of 40% HNO3 and 60% hydrofluoric
acid (HF) could be beneficial. Because HF is a weak acid, it does not completely ionize. The
metal surface is oxidized by NO2, and the tungsten oxide dissolves in HF, producing highly
soluble tungsten fluoride (WF6) or oxofluoride ions. Because there is no complexing agent,
such as fluoride, as in the previous acid combination, an oxide layer forms, that also slows the
reaction.
Even though, HF is a very responsive and unpleasant acid (extremely corrosive, causes
severe burns, and attacks bones hours after exposure). As a result, it should only be used by
experienced chemists who are familiar with its properties and are aware of the precautions to
be taken. The electrochemical performance of W in aqueous systems is tightly linked to two
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factors: W's strong affinity for oxygen, which always results in the formation of an irreparable
metal/metal oxide/metal ion system, and the complexity of W species in aqueous solution.
Notwithstanding the this, tungsten species in aqueous systems can react with polycarboxylic
acids such as oxalic, tartaric, or citric acid, which can be used to stabilize acidic tungsten
solutions (to prevent polycondensation) [33].
1.1.2.3 Production of Tungsten
The global average dispersion of W mining output from 2012 to 2016 is shown in (fig. 1-
2). Leading producer of principal W, accounting for 82 % (i.e. 73 000 t), with Vietnam as the
second largest manufacturer (i.e. 5 600 t (2015), contributing for only 4 %) [34, 35]
. With 60
percent of the world's W deposits. The next world's biggest reserves of W are in Canada (2%),
Russia and Vietnam (3 %), the United Kingdom (2 percent), Spain 1 (%), Austria (0.3 %),
Portugal (0.1 %), and other countries (22%). Because the United States, Bolivia, and Rwanda
are not included, some countries' worldwide distribution stocks show little variation across
surveys [36]
. Tungsten drilling is mostly done deep into the earth, with only a few exceptions
made for open-pit mining. Mines are typically small in size and are constrained by the size of
the ore bodies. More than 2000 tons of ore per day are done and the results, though mines
with rates of up to 5 500 tons of ore per day have lately been discovered. Globally traded ore
focuses involve 65–75 % WO3, implying that a huge proportion of ore must be mined just to
obtain a minimal quantity of W. To meet the international standards, a massive amount of
gangue material must be separated and typically deposited as tailings. As a result, ore
processing facilities are always placed near the mine to reduce operating costs [37]
.W demand
increased from 62,550 tons in 2005 to 82,500 tons in 2015. In 2015, China consumed the
most W (64%) followed by The UK (14%), the U.S. (9%), Japan (7%), and many others (6
%) [38]
. The rise in world market for W has been closely related to overall economic activity,
particularly the rise in China's GDP. Nevertheless, W consumption in Europe has been
declining by about 5% on average since 2002, owing to the fact that W goods are often used
in fully grown commercial processes rather than in novel and evolving technologies.
Thus, the reduction in W usage could be attributed to the low economic growth in
Europe, but demand for W in Europe appears to be slightly increasing since 2013 ,with a
[39]
propensity to continue. Despite the fact that ingestion of W continues to rise as the amount of
carbide tool production rises with the expansion of emerging markets [40]
, tungsten produced
in Europe, including mine production and end of life scrap recycling, could meet 80 percent
of demand . If Europe could fully utilize its primary and secondary resources, it would be
[41]
able to eliminate its reliance on other countries to produce hard metal tools [42].
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Global average dispersion output (%)

Fig.1-2: Global share of W mining production for 2012-present
1.1.2.4 Tungsten applications

The exceptional properties of W make it essential for application areas in harsh
environments. Tungsten has a broad range of applications, and latest research from the British
Geological Survey and USGS (2017), and it is demonstrated in four different main branches
for classifying modern W applications. Cemented carbide tool manufacturing is still the most
common use of W, accounting for approximately 54% of global average W consumption.
Tungsten implementations have progressed to include the manufacture of catalysts, electrical
and electronic components, and photocatalysis predicated on W-containing nanoparticles, as
well as electrocatalytic applications for fuel cells [35].
1.1.3 Cobalt
1.1.3.1 General properties of Cobalt
Cobalt (chemical element with symbol Co) is a silvery-gray metallic element with
essential properties such as strength, wear resistance when connected with other metals, low
electrical and thermal conductivity, high melting point (1493 °C), high higher stability, and
multivalences [4, 43].
Cobalt is also not discovered natural in nature, but instead in a variety of minerals and
substances that comprise it, however the major deposits differ in geologic, geochemical,
mineralogic, and other ways. Stratiform sediment-hosted Cu-Co deposits, Ni-Co laterite
deposits, and magmatic NiCu(-Co-PGE) sulfide deposits are the three main deposit types .
[4]
Cobalt is among the most abundant metals on the planet, with global resources estimated to be
around 7 million tons [44]. Despite the fact that this element is critical to the performance of the
products in which it is used, some efforts have been made to maintain it due to periods of high
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prices and growing concern about accessibility. However, replacing Co would result in a loss
of product performance and/or an increase in cost in many applications [45].
1.1.3.2 Chemistry of Cobalt
Table 1-5 lists the main chemical and physical properties of cobalt's inorganic materials
and structures. Cobalt is most commonly found in cobalt (II) and cobalt (III) compounds,
however there are infrequent Co compounds with +4, +1, 0, -1 oxidation states [43]
, Co (II)
compounds, in summary, dissolve in water. When cobalt is dissolved in dilute hydrochloric
acid (HCl), it produces cobalt (II) chloride, which has pink hues. This dissolves slowly, as
opposed to nitric acid (HNO3), which dissolves quickly and produces Co2+ ions as shown in
equation 1-1 and equation 1-2 [43]
Dilute HCl :Co+ 2 HCl →Co Cl2 + H 2 (1-1)

Dilute HN O 3 :3 Co+ 8 HN O3 → 3 Co¿ (1-2)
Another oxidation state of Co is +3, but this ion can only be discovered in complexes
because Co (III) ions are less steady than the other compounds. From neutral and alkaline
environments, pure Co releases oxygen. In HCl, all Co oxides dissolve. Co salts such as
cobalt (II) sulfate, cobalt nitrate, and cobalt (III) sulphate are common examples Co
compounds [43].
Table 1-5 General properties of cobalt (Co)
Cobalt Properties
Atomic Number 27 Atomic Mass 58.93 u
7 2
Electron Distribution [Ar]3d 4s Oxidation Number +2, +3
Melting Point 1495 C Boiling Point 2870 C
Electronegativity 1.8 Isotope 59
Density 8.9 g/cm3 Atomic Volume 6.7 cm3/mol
Ionization Energy 757.6 kJ/mol
1.1.3.3 Production of Cobalt

Cobalt is typically mined as a byproduct of much more abundant metals such as nickel or
copper, so manufacturing is driven primarily by the marketplaces for the main metals rather
than by the demand for Co. This situation limits the ability to adjust the amount of Co
extracted in reply to changes in the market and can result in periods of scarcity or oversupply
(as occurred from 2009 to 2015, once worldwide Co manufacturing surpassed usage, resulting
in a surplus market and downward pressure on prices) . Global annual Co utilization was
[4]
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roughly 75 000 metric tons in 2011; the top three Co consuming nations were China, Japan,
and the United States (in order of consumption amount). In 2016, estimated 126 000 metric
tons of cobalt (Co) were mined as ores, concentrates, and intermediate products from cobalt,
copper, nickel, transition metals element (PGE), and zinc processes [46].
Figure 1-3 shows the distribution of Co deposits based on global Co mine yield in 2011.
The Democratic Republic of the Congo (Congo Kinshasa or DR Congo) is the world's
primary source of mined Co. (55%). This country has the highest risk score for just doing
marketing due to poor infrastructure, resource nationalism, a high perspective of corrupt
practices, and a lack of accountability, as well as wars from the 1990s to the early 2000s,
living in a continual tension in the eastern part of the country with a significant risk of civil
conflict, which could also mean destabilization in Co supply. Even though civil unrest in the
eastern part of the Democratic Republic of the Congo has not impacted the Co-producing
areas, infrastructure issues (particularly energy and transportation) and reviews and
modifications to mining contracts have slowed some of the potential growth in mine
development and production. Nevertheless, the copper-cobalt mining sector in the Democratic
Republic of the Congo has strategy has worked from the production collapse that occurred in
the 1990s [47]. China has been the nation's top refiner of cobalt, with much of its output derived
from raw material imported from the Democratic Republic of the Congo. Australia, Belgium,
Canada, the Democratic Republic of the Congo, Finland, Norway, and Zambia were also
major source of refined Co. [48]
. The EU production is expected to be 2300 tons, with all of it
coming from Finland [49].
Congo (Kinshasa)
6% 6% Canada
6% 6% China
5% Russia
4% Other Countries
4% Zambia
Cuba
Australia
3%
3% Brazil
2% New Caledonia
55% Morocco
Fig.1-3 Pie chart of cobalt’s mine distribution by countries
1.1.3.4 Cobalt applications
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Cobalt's numerous applications can be classified into two broad categories: chemical and
metallurgical. Rechargeable batteries fall into the first category and have significantly
contributed to the fast expansion of Co demand, growing from 28% of total Co usage in 2010
to 49% in 2015 (Fig.1-4). Dyes, catalyst supports, dryers, as well as other minor chemical
end-uses account for less than 20%. The residual metallurgical end sectors include
superalloys, which accounted for 18% of total consumption in 2015, hard metals, magnet
alloys, hard-facing alloys, high-speed steels, and special alloys . Superalloys are used in
[17, 50]
high-temperature applications such as jet engines, gas turbines, space vehicles, nuclear
reactors, and power plants. Superalloys are classified into three types: cobalt-based alloys,
nickel-based alloys, and iron-based alloys. Because of its high melting temperature and larger
corrosion resistance at extreme temps, cobalt is used in superalloys as the matrix or as an
alloying element, and it is present in Co-based and nickel-based alloys, which account for 6%
and 80% of superalloy production, respectively. Cobalt-based forged alloys contain
approximately 30% Co, while Co-based cast alloys can comprise up to 65% Co. Over nickel-
based superalloys, cobalt-based superalloys have higher melting points than nickel (or iron)
alloys, superior resistance to hot corrosion in gas turbine atmospheres, and superior thermal
fatigue resistance and weldability [17].
0thers
Magnets
43.1% Tires/Paint dryers
17.24% Hard facing
catalysts
Ceramics/Pigments
Hard metals
Superalloys
8.62% Battery Chemicals
4.31%
6.9%
4.31%
6.03%
4.31%
5.17%
Fig.1-4 Refined cobalt demand by end-use in 2015
1.1.4 Tungsten Carbide

To gain a better understanding of tungsten carbide's (WC) characteristics, it is necessary
to outline quickly W's combination with oxygen and dioxide substances. A most extensively
used procedure for manufacturing WC is developed a tool of W powdered [51]
. A carbide that
combines the properties of both pottery and alloys is known as an intermediate cement. WC
powders can be synthesized in a variety of ways, but the two most common are carbothermal
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reduction of W oxide to pure W and subsequent carbonation of W (minimum particle size:

0.15– 12 m). To put it another way, WC's most common stage is cubic, which has a density of
15.63 grams/cm3, a normal boiling of 2870 degrees Celsius, and an equilibrium heating value
of 6100 degrees Celsius. Decomposition in W and C is possible at extreme temps; it begins at
atmospheric conditions of 500–600 °C. . Carburization temperatures for W powder and
[1, 52]
black C combinations typically vary from 1050 to 2100 degrees Celsius, based on the
powdery molecular weight. The influence of the properties of the starting materials (W and C)
as well as various more variables can account the vast maximum temperature, with the most
typical average temp being 1400–1600 °C. Carburization is also influenced by the quality of
W. Methods to deal is accelerated by ions such Co, however four appearances is slowed by
copper sulphate. [1, 53].
Tungsten carbide is exceptionally hard, with a Mohs toughness of roughly 9. Bonded
cement, that accounts for the vast majority of W usage globally, is made up of tiny corrosion
products cemented into a composite by an adhesive alloy. The incur heavy stages of WC are
held together by a ductile metallic phase (usually Co, but less frequently Ni or Fe mixtures)
the at encircle all. [1].Tungsten carbide-cobalt (WC-Co) is the most popular cemented carbide.
It's a compound substance composed of tungsten monocarbide particles implanted in a Co
matrix that's ideal for metal cutting, rock mining, and wear resistant operations. In the
manufacturing, mining, engineering, petroleum, and energy industries, they are commonly
employed. W is the most metallic of the cementite, and this compound normally includes 40–
95 percent of it[37, 54]
.The mechanical characteristics of WC-Co are determined by the Co
concentration and WC particle size, which may be modified to provide desired attributes for
particular purposes.[55].A greater Co concentration leads to less sharpness and more tenacity,
but a bigger yield strength enhances hardenability yet decreasing harshness. [56].
1.1.4.1 Tungsten carbide production
While China produces over 80% of the world's tungsten mines, the country produces
below half of the world's tungsten carbide, and just 23% of that was exported in 2015. [56].
W powder carbonization by high purity black carbon black, smoke, or paraffin is
generally done in two steps: first, highly pure W powder with desirable qualities is produced,
and then W powder is carbonized by different alloys black carbon black, soot, or carbon
fibers. The calcination stage is carried out by I ball grinding the W powder with carbon black,
soot, or graphene, and (ii) volatilized the W material in a nitrogen environment for 2-10 hours
at degrees of 1400-1600 °C.[54]. Many new W particle manufacturing technologies have
developed. The potential of WC manufacturing appears to be rapid decrease of tungsten oxide
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(WO3) or metal ore extract, which would eliminate the existing two-step manufacturing
methods (tungsten powder manufacture + calcination) in favor of a single-step approach.
Additional benefit of this new procedure is that it produces WC powder with a finer nanoscale
crystalline and better mechanical characteristic.[57].
1.1.4.2 Tungsten carbide applications
Due to their incredible wear resistance and high corrosion protection qualities, WC
metals have a variety of uses in numerous sectors, as shown in Fig.1-5. While tungsten
solidified with Cu or Ag is used for conductive material and fuel cells, tungsten carbide with
cobalt (WC-Co) is preferred for cutting tools due to its superior strength and durability,
strength properties, and capacity to endure warmer concentrations than typical high metal
equipment, as well as a sharper state of the art and dimensional accuracy. From the ball at the
tips of ballpoint pens to projectiles and antimissile warheads, WC is used for a variety of
things.[8].
The Co concentration of WC-Co hard metal tools and parts is typically around 6 and 16
wt%, however it can exceed 30 wt% in special cases. It corresponds to equipment needing
high hardness, such as those used in metal cutting, mining, and woodworking, in the instance
of 6 percent Co, and greater tenacity instruments, such as those used in cold rolling and hot
press, inside the case of 16 percent Co.[56].These leftovers must not be buried underground
after industrial usage to prevent pollution problems with dissolving Co, which is equally
harmful to human breathing systems.[58].
Fig.1-5 Distribution of WC applications for different sectors

1.1.4.3 Tungsten recovery
Since the global financial crisis in 2009, recycling activities in Europe have increased
significantly.
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According to experts, the recycling process for W in the EU could be as high as 45-50
percent. The recycling input rate from new and old scrap for W was estimated to be 35%, with
an end-of life recycling rate of up to 30% [59]. The excellent physical and chemical stability of
W, on the other hand, makes recycling extremely difficult [60]
. Recycling WC-Co hard metal
scraps can help to reduce their environmental impact, and there are numerous techniques for
performing recycling processes [8]. The recycling processes can be classified into different
categories based on the type of cemented carbide conversion method used:
➢ Methods that directly convert the provided material to powder of the same structure.
➢ Indirect techniques, which involve chemically modifying the element metals to
produce intermediate goods, which are then applied to generate pure metals;
➢ Semi-direct techniques in which one element is chemically dissolved while the
other phase(s) remains intact.
The binding metal is kept separate from the cemented carbide using the direct method,
while the binding metal is dissolved using the indirect method. Direct recycling techniques,
such as zinc or cold flow processes, are distinguished by their reduced energy consumption,
lower processing costs, and high carbide scrap recycling rate. Indirect recycling processes, on
the other hand, use acids and electrochemistry to dissolve the binder phase in cemented
carbide waste. This method consumes a lot of energy, has a lot of costs, and only recycles a
small amount of carbide scrap [61]
.Recycling of tungsten-bearing waste has been practiced
over several decades, with much R&D work committed to improving existing methods and
build new ones. However, more innovation capability in aspects of energy efficiency, cost
reductions, resource preservation, and environmental policy is still required .WC-Co waste
[7]
is typically recovered as a mixed powder of WC particles and Co binder, but some methods
attempt to recover W or Co selectively. Hydrometallurgical steps can be used to process WC-
Co particles, with prior oxidation of WC-Co waste increasing W dissolution or leaching
efficiency [62]
. Because alkaline solutions are used in conventional recycling, while W is
obtained as CaWO4, Co contained in the raw material is not recovered because Co is
precipitated in alkaline solution. As a result, there was an urgent need to develop an
environmentally friendly recovery process for W and Co that combined unheated oxidation,
room temperature, and pressure leaching [63]
. The emphasis of this work is on one of these
methods under development, electrochemically based techniques. The main WC waste
recycling methods will be summarized next.
I. Zinc process
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On an industrial scale, the zinc recycling process is the most widely used direct recycling
process of cemented carbide . The WC scrap excess heat (900-950 °C) is aided by the
[8]
addition of argon gas and is then vacuum distilled. The preferential dissolution of Co-occurs
at high temperatures (800 °C) in a molten Zn bath, accompanied by Zn evaporating
(distillation process) at around 950 °C in an inert atmosphere. Cobalt precipitation occurs as a
result of its high melting point (1495 °C as opposed to Zn's 950 °C). A finely divided WC
material is obtained after selective dissolution of Co from the matrix. There is a significant
amount of energy consumed; approximately 4000 to 6000 kWh are required for only one ton
of WC [64].
II. Cold stream process
The cold stream process, like the zinc process, necessitates a lot of energy and expensive
specialized equipment. The cold stream flow process requires heating cemented carbide scrap
to a high temperature, then injecting a high-speed cold air flow into the scrap to break and
separate it, and finally recovering WC [65].
III. Chlorination process
The WC-Co scrap is first chlorinated (exposed to a chlorine atmosphere at high
temperatures) to form metal chlorides in this recycling process. They can then be subjected to
two steps: Mechanical reduction for the production of WC powder; or acidic/alkaline leaching
to obtain intermediate byproducts such as ammonium para-tungstate, ammonium tungstate, or
tungstic acid [66].
IV. High-temperature oxidation process

The inflammation in scrap materials is caused by a high-temperature process carried out
at temperatures above the melting of the binder phase. The porous mass of WC is obtained,
and then a mechanical reduction operation is performed to acquire the very fine powder of
WC. However, this process necessitates a significant power usage [8].
V. Hydrometallurgical process
Immersion of WC materials in leaching solution dissolves the binder material and leaves
the WC residue in hydrometallurgical recycling. Grinding operations are performed on this
material before it is reused in the production of WC components. The hydrometallurgical-
based recycling process, on the other hand, is primarily for grinding sludge, W-Cu, soft
scraps, and solid scraps that can be treated by various acidic/alkaline media. Binder materials
are typically leached from WC materials. After optimizing the various leaching parameters
(temperature, pressure, and pH of the solution, stirring speed, and strength of the leaching
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solution), the leaching process can be accelerated in the strong acid/oxidizing environment
(aqua-regia/H2O2). Because of the significant separation and purification steps required to
obtain a pure form of the product, hydrometallurgical recycling is generally more expensive
than direct recycling. However, selective Co leaching can reduce the number of steps and
improve the process's energy efficiency [8, 67].
VI. Electro-dissolution/ Electrochemical process
Although the zinc procedure and cold stream process are the most common recycling
techniques, electro-based technologies have been produced in parallel. Electrometallurgical
methods of recycling WC scrap (electrochemical, electro dissolution, anodic dissolution,
anodic leaching/electro-leaching techniques, or electrowinning) are one-step processes using
less energy depending on the electrolytes used. When particularly in comparison to other WC-
Co waste recycling methods, electro dissolution techniques currently provide very pure results
[68]
. The electro-dissolution procedures is used to recycle WC-Co waste, in which scrap WC-
Co acts as an anode and graphite/stainless steel acts as a cathode, with both anode and cathode
submersed in the electrolyte (acid/alkaline) during in the electrochemical reaction. The
spacing between the anode and cathode, as well as other electrochemical parameters, are
optimized to reduce energy consumption and increase cell efficiency, and the electrolytes can
be regenerated and reused after minor changes (e.g., pH). After supplying power to the cell,
an electrochemical reaction occurs: the positive power supply is connected to the anode, and
the negative power supply is connected to the cathode. As a result, once the anodic dissolution
of the waste material begins, Co migrates to the solution and deposits on the cathode, while
the remaining carbides break and fall to the cell's bottom [8].
However, because anode passivation reduces process efficiency and limits electro
dissolution, increasing productivity of anodic dissolution techniques is a major concern for
researchers. In addition to addressing the passivation issue, researchers are working to reduce
the number of steps required to make the final product. Various reagents (electrolytes) of
varying concentrations have been tested in this context in order to develop a simpler and more
efficient process. These are the acid-based reagents with low pH (HCl (Fig.1-6), HNO 3,
H2SO4, and H3PO4) and the alkaline based reagents with high pH (NaOH and NH4OH) [8].
第 19 页/共 51 页
Fig.1-6 Process flow chart for the WC recycling using electro-dissolution in acidic media
1.1.4.4 Sustainability of the tungsten carbide recycling industry

According to research and projections, WC scrap will continue to be an increasingly
important source of raw material for the global tungsten industry . According to statistics,
[69]
recovering W and Co from WC scrap accounts for approximately 20% to 30% of total supply,
lowering raw material costs by 15% to 50% . The substitution of tungsten-based cemented
[8]
carbides it seems to be technically feasible, but it assumes higher costs and a decrease in
quality in some cases, as W has very special properties and is usually the best material choice.
Moreover, cemented carbides based on other CRMs, such as niobium or titanium carbide, are
potential substitutes for cemented tungsten carbides (also a CRM for EU and USGS).
Ceramic-metallic composites are also being researched, but the technology is not yet
competitive [70]
. Energy efficiency is a significant cost driver for any process, with a
meaningful effect on the profit margins of a business operation, and optimizing WC recovery
while keeping energy costs as low as possible is no exception. One of the major advantages of
the zinc recycling process (a direct method) a few decades ago was that it used three times
less energy to produce virgin WC than the indirect conversion methods. Nevertheless, due to
the high cost of energy in various countries, the zinc process has become an energy-intensive
and costly process that is considered unfavorable. The trend of WC recycling in the future
will favor less energy-intensive recycling processes [71].
A global view of the WC recycling industry, such as future trends, is essential for
analyzing the progression of the sector's sustainability. As previously stated, Chinese
production and exports dominate global W supply, with rising expectations for the coming
years. According to the International Tungsten Industry Association (ITIA), China has
imposed stricter regulations and export taxes on the W industry. This applies not only to
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primary tungsten mines and tungsten concentrates produced as a by-product of other metal
mining, but also to tungsten by-products such as tungsten carbide. It prompts several
companies to restart W mines or develop new W deposits in Europe, North America, Asia,
and Australia, potentially changing the WC industry's paradigm [65, 72].
1.1.5 Anodic passivation
Anodic passivation (AP), also known as Anodic Control, is a method for controlling the
corrosion of a metal surface by converting it into the anode of an electrochemical cell and
controlling the electrode potential in a zone where the metal is passive [73]
. Anodic passivation
is used to protect passivated metals in environments where the concentration in the freely
corroding state is significantly higher than the current density in the passive state over a wide
range of potentials [73]. Anodic passivation can also be used in carbon steel storage tanks with
extreme pH situations, such as concentrated sulfuric acid and 50% caustic soda, where
cathodic protection is not appropriate due to extremely high current requirements [74]
. Anodic
passivation also keeps a metal at a fixed potential in relation to a reference electrode. One of
the potentiostat's three terminals is connected to the tank to be protected, another to an
auxiliary cathode (platinum), and the third to the reference electrode. As a result, a
potentiostat keeps the potential between the tank and the reference electrode constant [75].
1.2 Electrochemical Process
1.2.1 Principles of electrochemical process
The electrochemical (EC) process was invented in 1992 at the Technical University of
Denmark and was patented in 1995 (PCT/DK95/00209). The electrokinetic (EK) corrective
method is combined with electrodialysis in the ED remediation technique, which is based on
the application of a low-level direct current . The electrochemical (EC) and electrokinetic
[4]
(EK) corrective methods are similar, except that EC utilizes ion exchange membranes to
differentiate the polluted matrix from the electrode compartments, whereas EK uses passive
membranes [76]
. Ion exchange membranes improve removal efficiency due to their good
conducting properties, lowering power consumption and providing good chemical stability
over a wide pH range [77]
. In practice, EC technology is an optimization of the EK process ,
[78]
that has been developing to removal of toxic from a variety of environmental matrices,
including sludges, fly ashes, timber waste, and mine tailings [79].
Water electrolysis (which causes pH changes) is one of the most important reactions that
occur during the EC process, but several other reactions occur during the treatment. There are
two main removal mechanisms in an EC cell where the matrix to be treated is placed in a
stirred suspension, as is the case in this work: electromigration and electrodialysis. These
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reactions and mechanisms will be discussed further below. However, when the EC process is
carried out in a stationary system, there are many transport mechanisms (similar to EK), such
as electroosmosis (the mass flow of pores in relation to soil particles under the influence of an
electric potential gradient); electrophoresis (the movement of charged colloids under the
application of an electric field); and diffusion (the movement of species in areas with high
chemical concentrations) [80].
1.2.1.1 Reactions in the electrode compartments
The EC process is made up of several interacting mechanisms, the most important of
which is water electrolysis, which is represented in the equations 1-3 and 1-4 and Fig. 1-7a-b
as the dominant electron transfer reaction that occurs at electrodes [45].
−¿¿
Anodic :2 H 2 O →O 2 ↑+4 H +¿+ 4 e ¿

(1-3)
−¿¿
−¿→ 2 H 2 (g)↑+4 OH ¿
Cathode : 4 H 2 O+ 4 e (1-4)
Fig.1-7 Schematic representation of a 3-compartment cell used for ED experiments applied to a stirred
suspension of a solid matrix (a) vs 2-compartment cell (b)
1.2.2 W and Co recovery through EC process

The use of EC for WC-Co treatment is a semi-direct method because the supplied
material must be converted to powder of the same structure (direct phase) before beginning
the electrochemical dissolution of one component while leaving the other phase intact
(indirect phase). As previously stated, tungstate anion (WO4 2-
) and cobalt cation (Co2+, 3+)
are generated in the respective electrolytes all through anodic dissolution. The anode is
typically sacrificed in anodic dissolution, but this technique was not used in our work. To
support the dissociation of W and Co from tungsten carbide, we subjected a WC-Co waste
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powder to acid dissolution, followed by electromigration and electrodialysis to separate the

Co from the W [81]
. Nevertheless, some Co is expected to be stored on the cathode in both
cases, while a small amount of disintegrated tool matrix may remain at the bottom of the
electrolytic cell, which could be undissolved WC that precipitates during the Co dissolution
from tungsten carbide . Aside from the very specific properties of tungsten, this method is
[82]
extremely difficult due to the different behavior of Co and W.

Almeida et al. (2020a) and Rosário (2018) investigated the use of the EC process for W
recovery from mine tailings while also removing arsenic (As) in a 3C cell . Because the
[52]
mine tailings were not treated, the matrix was much more complex than the WC carbide
matrix, which was the focus of this work. The preliminary findings revealed some difficulties
in W recovery due to the low migration rate of W to the electrolyte compartment, which could
be increased using a 2C ED cell. However, when working with a different matrix, we need to
analyze the Co and W behavior, so we started with the 3C cell.
1.2.3 Potentiodynamic polarization
Potentiodynamic polarization is a polarization technique wherein the potential of the
electrode is differed at a predetermined rate over a relatively large potential domain by
passing a current through the electrolyte [83]. For laboratory corrosion testing, potentiodynamic
polarization is frequently used. It can provide valuable information about corrosion
mechanisms, corrosion rates, and the susceptibility of specific materials to corrosion in
specified environments. Potentiodynamic polarization is another name for potentiodynamic
polarization [84].
Is also a technique in which the potential of an electrode is varied at a predetermined rate
by passing a current through the electrolyte. This method is used to polarize specimens for
corrosion testing. Cyclic voltammetry is a potentiodynamic polarization variant that involves
sweeping the potential in a positive direction until a predetermined value of current or
potential is reached. The scan is then reversed toward more negative values until the original
potential value is reached. The cyclic polarization test is the most widely used variant [85]. This
test is frequently used to determine a material's pitting susceptibility. The potential is typically
swept in a single cycle or slightly less than one cycle, with the scan beginning at the corrosion
potential. This technique has proven particularly useful in assessing localized corrosion in
passivating alloys such as S31600 stainless steel, as well as other alloys such as titanium and
zirconium [86]
. Although the generation of the polarization scan is straightforward, its
interpretation can be challenging.
1.2.4 Chrono-potentiometric
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Chrono-potentiometry [87]
is a galvanostatic method that maintains a constant current at
the working electrode for a set period of time [88]
. The potential and current of the working
electrode are measured as a function of time. This method is used by researchers to
investigate the mechanisms and kinetics of chemical reactions. It is also commonly used in
the study of batteries and electrodeposition. CP is typically performed in an unstirred
electrochemical cell; however, some researchers combine CP with rotating electrodes.
However, current is typically kept constant between both the working and counter electrodes,
while potential is evaluated at the electrode surface relative to the reference electrode .
[89]
Redox-active species diffuse to the working electrode surface to balance the applied current
until the diffusion-limited concentration of redox species reaches zero at the electrode surface,
at which point potential changes to the redox potential of the next species in solution, if any
are present (which could be solvent). CP is also frequently used in battery charging and
discharging experiments . Chronopotentiometry is also used to investigate the mechanism
[90]
and kinetics of chemical reactions. The instrument in this technique continues to operate in
galvanostatic mode to control current and measure voltage. The applied current can be either
single or double stepped. It is usually done in a quiet (unstirred) solution.
Chronopotentiometry In most cases, constant-current chronopotentiometry is used, in
which a constant current is applied to the working electrode, causing the electroactive species
to be reduced at a constant rate.
1.2.5 Chrono-amperometric
Chrono-amperometric is an electrochemical process in which the working electrode's
potential is decided to step and the resulting current from faradaic processes occurring at the
electrode (caused by the potential step) is measured as a function of time . After applying a
[91]
single or double potential step to the electrochemical system's working electrode, the
functional relationship between current response and time is measured. The peak oxidation
current versus peak reduction current ratio can provide some information about the identity of
the electrolyzed species [92]
. However, chronoamperometry, like all pulsed techniques,
generates high charging currents that decay exponentially with time, just like any circuit. The
Faradaic current, which is caused by electron transfer events and is frequently the current
component of interest, decays according to the Cottrell equation. This decay is much slower
in most electrochemical cells than the charging decay-cells with no supporting electrolyte are
notable exceptions. A three-electrode system is most commonly used [93]
. Because the current
is integrated over relatively longer time intervals, chronoamperometry has a higher signal-to-
noise ratio than other amperometric methods.
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1.3 Research significance, Content, Innovation point and Technical Route

1.3.1 Research significance
Anodic passivation during electrochemical process for cemented carbide scrap have
raised some concern especially when it comes to the dissolution stage and even the recovery
of tungsten carbide during this process. Tungsten carbide recovery in alkaline solution during
this process are sometimes not recovered due to the precipitation in the solution. The use of
acidic solution in the passivation of anodes during electrochemical process and also for the
recovery of tungsten have been seen substantial, due to its environmentally friendly recovery
process. However, based on this study, the innovation discloses an experimental analysis on
anodic passivation constant voltage for cemented carbide scrap and investigating the constant
current in anodic passivation during electrochemical dissolution.
1.3.2 Research content
Based on the above research ideas, this subject is intended to carry out research from the
following aspects:
(1) Analyzing anodic passivation constant voltage for cemented carbide scrap:
Firstly, a method to analyses the constant voltage during anodic dissolution has been
investigated by dissolving the cobalt scrap in hydrochloric acid (HCl) solution at specific time
intervals with a constant current.
(2) Investigating the constant current in anodic passivation during electrochemical
dissolution:
During the same process when the cobalt scrap was dissolved in the HCl solution, the
constant current was also evaluated using the constant voltage.
1.3.3 Innovation point
Based on the mixture or dissolution of the cobalt scrap in the solution for analyzing both
the constant voltage and constant current through electrochemical process, it was discovered
that the method has great has great application potential and the following beneficial effects:
1) It was found that the time changes, the voltage remained constant even after the
reached 24 h, and the solution had no effect on the constant voltage at the moment.
2) It was also found that when the time was changing at different intervals, the current
remained constant even after the time interval reached 24 h.
1.3.4 Technical route
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Figure 1-8 Research idea of the study
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CHAPTER 2: MATERIALS AND METHODS
2.1 Experimental materials and methods

2.1.1 Experimental materials
The main reagents and instruments used in this experiment are shown in Table 2-1 and 2-
2 respectively.
Table 2-1 Experimental reagents
Reagent name Purity Manufacturer
Sulfuric acid (H2SO4) GR Hengyang Kaixin Chemical Reagent Co., Ltd.
Hydrochloric acid (HCl) AR Sinopharm Chemical Reagent Co., Ltd.

Table 2-2 Experimental equipment
Equipment name Model Manufacturer
Precision electronic balance EL104 Hitler-Toledo Instruments
Co., Ltd.
X-ray diffractometer D8-Advance Bruker AXS GmbH Co., Ltd
pH meter control PH5-3E INESA Leici Co., Ltd
2.1.2 Cobalt scrab dissolution preparation (Set-up)

Cobalt Scraps (CS) of machine-grade cemented tungsten carbide were taken as raw
material for this work. The composition and size of carbide particles are listed in Table 2-3.
Scraps, cut to an adequate size and shape by spark machining, mounted with epoxy resin to
expose an area of 2100 mm2 (10 × 10 mm), were used as the working electrode. In the process
of selective electrolysis and the dissolution preparation of the scrap, the scrap carbide
(containing 6% cobalt and 94% tungsten) was used as anode and was placed into a solution of
dielectric-hydrochloric acid (HCl) under the action of direct current field connected to the
power station that contains both the cathode and the anode cord (which the scrap is attached)
in the first experiment and was also placed into sulfuric acid during the second experiment.
After that, the bonded phase metal drill was oxidized on the anode and became divalent
cation. A schematic illustration of the preparation process is shown in fig.2-1.
Table 2-3 Composition and grain size of the cemented tungsten carbide scrap
Sample Composition (Wt%) Grain Size (μm)
Co WC
CS 6 94 2
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Fig.2-1 Cobalt scrap dissolution preparation process
2.1.3 Preparation of HCl and H2SO4

2.1.3.1 Hydrochloric acid (HCl) preparation
The preparation of hydrochloric acid (HCl) involves the combination of deionized water
and hydrochloric acid, in order to achieved 0.1, 0.2, 0.3 and 0.4 molar solution of 37%
hydrochloric acid (HCl). Firstly, 4.16ml, 8.33ml, 12.5ml and 16.67ml of hydrochloric acid
(HCl) was placed and prepared separately in a volumetric flask containing 500 mL deionized
water. After the flask was shaken in order to obtain a balance concentrated solution.
2.1.3.2 Sulfuric acid (H2SO4) preparation
The preparation of sulfuric acid (H2SO4) involves the combination of deionized water
and sulfuric acid (H2SO4), in order to achieved 0.1, 0.2, 0.3 and 0.4 molar solution of 97%
sulfuric acid (H2SO4). Firstly, 2.7ml, 5.49ml, 8.24ml and 10.99ml of sulfuric acid (H 2SO4)
was placed and prepared separately in a volumetric flask containing 500 mL deionized water.
After the flask was shaken in order to obtain a balance concentrated solution.
2.1.4 Experimental design
The experiment was carried out in order to conduct six (6) different comparison and
investigation using constant voltage and constant current with their experimental variation
analyzed at different time interval (30, 60, 120, 240 360, 480 and 1440 mins). A summary of
the detailed experimental design is as follows:
a. Constant voltage: Anodic current + HCl solution
b. Constant voltage: Anodic current + H2SO4 solution
c. Constant Voltage: Anodic current + HCl + H2SO2 solutions combine
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d. Constant Current: Voltage variation + HCl solution

e. Constant Current: Voltage Variation + H2SO4 solution
f. Constant Current: Voltage Variation + HCl + H2SO4 solution
2.1.5 Constant voltage experimental procedure using (HCl and H2SO4)
2.1.5.1 Constant voltage with anodic current variation procedure (HCl)
In the experiment procedure of constant voltage, the voltages were adjusted to different
constant voltages (0.5, 0.75, 1, and 1.25) using the power station while utilizing hydrochloric
acid (HCl) solution with concentration of 0.1, 0.2,0.3 and 0.4 molar solution, in order to
obtain different variation of anodic current at different time intervals of (30, 60, 120, 240 360,
480 and 1440 mins).
2.1.5.2 Constant voltage with anodic current variation procedure (H2SO4)
The voltages were changed to different constant voltages (0.5, 0.75, 1, and 1.25) using
the power station while employing sulfuric acid (H 2SO4) solution with concentrations of 0.1,
0.2, 0.3, and 0.4 molar solution, in order to obtain different variations of anodic current at
different time intervals of (30, 60, 120, 240 360, 480 and 1440 mins).
2.1.5.3 Constant voltage with anodic current variation procedure (HCl and H2SO4)
In the constant voltage experimental procedure, the voltage was maintained to the
constant voltage of 1 V, using the power station, and the analysis of both hydrochloric acid
(HCl) and sulfuric acid (H2SO4) solution with concentration of 0.3 molar solution were
compare in order to obtain different variations of anodic current at different time intervals of
(30, 60, 120, 240 360, 480 and 1440 mins).
2.1.6 Constant current experimental procedure using (HCl and H2SO4)
2.1.6.1 Constant current with Voltage variation procedure (HCl)
The current was changed to different constant currents (0.1, 0.2, 0.5 and 1) while using a
power station and hydrochloric acid (HCl) solution with concentrations of 0.1, 0.2, 0.3, and
0.4 molar solution to obtain different variations of anodic current at different time intervals
(30, 60, 120, 240 360, 480 and 1440 mins).
2.1.6.2 Constant current with Voltage variation procedure (H2SO4)
In the procedure for analyzing constant current, the constant current was changed to
different constants (0.1, 0.2, 0.5 and 1) using the power station while using sulfuric acid
(H2SO4) solution with concentrations of 0.1, 0.2, 0.3, and 0.4 molar solution, in order to
obtain different variations of voltage at different time intervals (30, 60, 120, 240 360, 480 and
1440 mins).
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2.1.6.3 Constant current with Voltage variation procedure (HCl and H2SO4)
In the experimental procedure for analyzing constant current, the constant current was
changed to different constant (0.1, 0.2, 0.5 and 1) using the power station while using the
mixture of both hydrochloric acid (HCl) and sulfuric acid (H 2SO4) solution with
concentrations of 0.1, 0.2, 0.3, and 0.4 molar solution, in order to obtain different variations
of anodic current at different time intervals of (30, 60, 120, 240 360, 480 and 1440 mins).
2.2 Tungsten Cobalt scrap characterization
The crystal structure of the of the cobalt scrap was evaluated before being placed in the
both acid solution and after it have been dissoluted in the solution using X-ray diffractometer
(XRD) (Bruker-D8-Advance).
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CHAPTER 3: CURRENT VARIATION OF COBALT SCRAP

ANALYSIS AT DIFFERENT CONSTANT VOLTAGES (CV)
3.1 Introduction
Cemented tungsten carbide with cobalt binder is used extensively in the manufacture of
cutting and drilling tools, and high wear-resistant parts [94]
. When the tools and components
are scrapped, they are collected with a view to recovering the tungsten and cobalt in light of
the strategic importance of these metals . Statistics reveal that recovered tungsten carbide
[69]
comprises about 20 to 30% of the total supply, lowering the raw material cost by about 15 to
50% . Tungsten carbide is commonly used in cutting tools, drilling tools, machining tools,
[94]
and wear resistant parts. W and Co uses scraps of WC tool bits and their components as a
secondary resource [94]
. The analysis of constant voltage has been seen and investigated in
many studies and a lot of comparison were brought up. In the variation of different anodic
current flow at specific voltage, there have been decrease and sometimes increase in
magnitude of the current flow at those chosen voltages.
The analysis of anodic passivation in the presence of either HCl and H 2SO4 has been
utilized in previous studies and the anodic passivation has sometimes retards the acid
dissolution of the cobalt. Anodic passivity of the scrap in acids has demonstrated many
different effects and its explain and discussed in details in this chapter. Electrochemical
methods have been studied to recover the tungsten from cemented carbides by either complete
or selective electrolysis [8]. however, selective electrolysis is a potential alternative in view of
its lower energy consumption and environmental impact. Selective electrolysis seems to be
more competitive because of process, and low energy consumption [95]
. However, anodic
passivation is the main drawback which inhibits the dissolution of the binder phase. A novel
process recently has been developed by the authors to solve this problem [8].
In this chapter, the analysis of anodic current variation was investigated at different
constant voltages in hydrochloric acid and sulfuric acid solution.
3.2 Results and discussion

3.2.1 Constant Voltage analysis
After experimental procedures, various constant voltages were selected to investigated
the variation of anodic current in HCl, H 2SO4 and in the combine mixture of HCl and H 2SO4,
and the results are displayed in the following session.
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3.2.1.1 Variation of anodic current with time in HCl solution

The variation of anodic current with different time intervals (30, 60, 120, 240 360, 480
and 1440 mins) in the presence of Hydrochloric acid (HCl) at the constant voltages of (0.5,
0.75, 1, and 1.25) is shown in (Fig.3-1a-e). As seen in Fig.3-1a, the variation of current flow
with time for the electrolysis of scrap at 0.5 V in 0.1M Hydrochloric acid (HCI) solution
without the presence of sulfuric acid (H2SO4), decreased steeply with time in the first 8 h
from (0.035-0.011), and then gradually over the next 24 h, and this is due to the presence of
concentrated acid with the scrap which was also seen in previous studies . Fig.3-1b also
[96]
shows a decrease in the current variation from (0.040-0.018) as the time increases and reached
the maximum of time of 24 h utilizing the constant voltage of 0.75 V in 0.2M Hydrochloric
acid (HCI) solution without the presence of sulfuric acid (H2SO4). Fig.3-1c also despites the
same results with decline in the current variation from (0.18-0.06) using 0.3 M of
Hydrochloric acid (HCI) solution at the constant voltage of 1 V. The decline of the current
magnitude from (0.11-0.02) was also demonstrated in Fig.3-1d with the utilization of 0.4 M
Hydrochloric acid (HCI) solution at the constant voltage of 1.25 V, which has been evidence
in recent study[97].To summarized the full occurrence of these variation, the magnitude of the
current for the scrap electrolyzed at 0.5 V was smaller than at 0.75 V, 1.25 V and 1 V since
passivation in the former is much easier with reference to Fig. 3-1e. This concludes that the
scrap at 0.5 V has more chance to suffer passivation than the rest.
（a）Current variation using 0.1M HCl (b) Current variation using 0.2M HCl
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(c) Current variation using 0.3M HCl (d) Current variation using 0.4M HCl
(e) Current variation using all four voltages

Fig.3-1 Comparison of current variation using various constant voltages in different HCl concentration
3.2.1.2 Anodic current variation with time in H2SO4 solution

The alteration of anodic current with various time intervals (30, 60, 120, 240, 360, 480,
and 1440 mins) in the appearance of sulfuric acid (H 2SO4) at constant voltages of (0.5, 0.75,
1, and 1.25) is shown in figure (Fig.3-2a-e). As shown in Fig.3-2a, the discrepancy of current
with time for scrap electrolysis at 0.5 V in 0.1M H 2SO4 solution even without presence of
concentrated Hydrochloric acid (HCI), decreased sharply in the first 8 hours and then
gradually over the next 24 h, which is due to the presence of scrap in acidic solution. Fig.3-2b
as well shows a decrease in current variation as time passes, reaching a maximum of 24 h
when using a constant voltage of 0.75 V in a 0.2M sulfuric acid (H 2SO4) solution without the
presence of Hydrochloric acid (HCI). Fig.3-2c demonstrates the same results with a decrease
in current variation when using 0.3 M H2SO4 solution at a constant voltage of 1 V. The
decrease in current magnitude was also shown in Fig.3-2d when a 0.4 M sulfuric acid (H 2SO4)
solution was used at a constant voltage of 1.25 V.
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To clarify the full range of these variations, the current that flows for the scrap
electrolyzed at 0.5 V was lower than at 0.75 V, 1.25 V, and 1 V because passivation is much
easier in the former (Fig. 3-2e). This means that the scrap at 0.5 V has a higher chance of
passivation than the others.
（a）Current variation using 0.1M H2SO4 (b) Current variation using 0.2M H2SO4
(c) Current variation using 0.3M H2SO4 (d) Current variation using 0.4M H2SO4
(e) Current variation using all four constant voltages

Fig.3-2 Comparison of current variation using various constant voltages in different H 2SO4 concentration
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3.2.1.3 Comparing Current variation with time in HCl and H2SO4 at (1V)
The variation of anodic current with different time intervals (30, 60, 120, 240 360, 480
and 1440 mins) for hydrochloric acid (HCl) and sulfuric acid (H 2SO4) at the constant voltages
of (1 V) were compare, and is shown in (Fig.3-3). As seen in Fig.3-3, the variation of current
with time for the electrolysis of scrap for 0.3M of Hydrochloric acid (HCI) and sulfuric acid
(H2SO4) solution, decreased steeply with time and then gradually over the next 24 h. This has
also proven evident with HCl having higher variation than H 2SO4 and other acids in the
presence of the cobalt scrap[98]. However, due to the down-trill of the current flow, the scrap at
1 V for H2SO4 has more chance to suffer passivation than the scrap at 1V HCl. In general, the
selective dissolution of the Co binder from the scrap was efficient, when it was electrolyzed at
1V in 1 3M HC1 and the anodic current in the H 2SO4 system was smaller than in the HCI
system.
Fig.3-3 HCl and H2SO4 comparison in current variation at (1V)
3.3 Summary
This chapter investigated the variation of anodic current with time utilizing different
voltages ranging from (0.5 V-1.25 V) in hydrochloric acid (HCl) and sulfuric acid (H 2SO4).
The comparison of both solution at the constant voltage of 1V were also analyzed. The main
conclusion are as followed:
1) When the time increases from (30-1440mins), there was a decrease in the variation
2) The high level of anodic current variation was achieved at the constant voltage of
1V for both solutions.
第 35 页/共 51 页
3) When both solution anodic current variation was compare at the constant voltage of
1, HCl still prove to be efficient for the scrap electrolysis process than H2SO4.
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CHAPTER 4: VOLTAGE VARIATION OF COBALT SCRAP

ANALYSIS AT DIFFERENT CONSTANT CURRENT (CC)
4.1 Introduction
The scrap of tungsten carbide is widely used in the production of cutting and drilling
tools, as well as high wear-resistant parts [94]. Because of the strategic significance of these
metals, scrapped materials and techniques are collected in order to regain the tungsten and
cobalt. According to statistics, tungsten carbide has been used and analyzed in over 80% of
the research conducted in metallurgy today. Tungsten carbide is also a material that
uses machining tools, and wear resistant parts. The Scraps of WC metal parts and their
elements are used as a secondary source of income by W and Co. Numerous research findings
have seen and explored the assessment of constant current, and so many comparisons have
been made[99]. There has been a increase and sometimes a decrease in the variation magnitude
of the voltage flow at specific constant current with different time intervals. The process of
analyzing the scrap electrochemically has been researched in recovering the tungsten from
cemented carbides either through one of the electrolysis processes. However, because of its
lower energy usage and ecological consequences, selective electrolysis is a viable alternative.
Due to the sheer process and low energy consumption, selective electrolysis appears being
more able to compete . The main disadvantage that prevents the dissolution of the binder
[100]
phase is anodic passivation. Some studies have recently developed an innovative procedure to
address this issue. Earlier studies have been using anodic passivation in the appearance of
either HCl or H2SO4, and the anodic passivation occasionally delays the acid dissolution of
the cobalt. The anodic passivity of scrap in acids has proved a variety of effects, which are
explained and mentioned in detail in this chapter. In this chapter, the analysis of voltage
variation was investigated at different constant current in hydrochloric acid and sulfuric acid
solution.
4.2 Results and discussion
4.2.1 Constant Current analysis
Following the completion of the experimental procedures, various constant currents were
chosen to investigate the variation of voltage in HCl, H2SO4, and the combined mixture of
HCl and H2SO4, and the results are shown in the following session.
4.2.1.1 Variation of voltage with time in HCl solution
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The variation of voltage with different time intervals (30, 60, 120, 240, 360, 480, and
1440 mins) in the presence of Hydrochloric acid (HCl) at constant current of (0.05, 0.15, 0.1
and 0.2) is shown in the figure (Fig.4-1a-e). The variation of the voltage flow with time for
the electrolysis of scrap at 0.05 current in 0.1M Hydrochloric acid (HCI) solution without the
presence of sulfuric acid (H2SO4) increase steeply with time in the first 2-5 h from (1.59-
1.80), and then gradually over the next 24 h, as shown in Fig.4-1a. Fig.4-1b also shows
an increase in voltage variation from (2.1-2.2) as time increases, reaching a maximum of 24 h
using a constant current of 0.15 in a 0.2M Hydrochloric acid (HCI) solution without the
presence of sulfuric acid (H2SO4). Fig.4-1c shows the same results with a increase in voltage
variation from (2.0-2.1) when using 0.3 M of Hydrochloric acid (HCI) solution at a constant
current of 0.1. The increase in voltage magnitude from (1.9-3.4) was also shown in Fig.4-1d
when a 0.4 M Hydrochloric acid (HCI) solution was used at a constant current of 0.2. This
increase of voltage has also been also been shown in previous study with the utilization of
HCL solution[101].To conclude the full range of these variations, the magnitude of the voltage
flow for the scrap electrolyzed at 0.05 was lower than at 0.1, 0.15, and 0.2 current, because
passivation is much easier in the former (Fig. 4-1e). This means that the scrap at 0.05
current has a higher chance of passivation than the others.
（a）Voltage variation using 0.1M HCl (b) Voltage variation using 0.2M HCl
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(c) Voltage variation using 0.3M HCl (d) Voltage variation using 0.4M HCl
(e) Voltage variation using all four voltages

Fig.4-1 Comparison of voltage variation using various constant current in different HCl concentration
4.2.1.2 Voltage variation with time in H2SO4 solution

the variation of voltages with time intervals (30, 60, 120, 240, 360, 480, and 1440 mins)
in the presence of sulfuric acid (H2SO4) at constant current of (0.05, 0.15, 0.1, and 0.2) (Fig.4-
2a-e). As shown in Fig.4-2a, the discrepancy of voltage with time for scrap electrolysis at 0.05
current in 0.1M H2SO4 solution, even in the absence of concentrated Hydrochloric acid (HCI),
increase sharply in the first 6-8 h from (1.6-1.7 V) and then gradually over the next 24 h,
which is due to the high concentrated acid [102] Fig.4-2b also shows a increase in
voltage variation over time from (2.0-2.1), reaching a maximum of (3.0) voltage at 24 h when
using a constant current of 0.1 5 V in a 0.2M sulfuric acid (H 2SO4) solution without the
presence of Hydrochloric acid (HCI). Fig.4-2c shows the same results but with high
voltage variation when using a 0.3 M H2SO4 solution at a constant current of 0.1. The
increase in current magnitude from (2.4-3.1) from 5-8 h was also shown in Fig.4-2d when a
0.4 M sulfuric acid (H2SO4) solution was used at a constant current of 0.2.
第 39 页/共 51 页
To demonstrate the full range of these variations, the voltage that flows through the scrap
electrolyzed at 0.05 current was lower than at 0.1, 0.15, and 0.2 current because passivation is
much easier in the former (Fig. 4-2e). This means that the scrap at 0.05 V is more likely to
passivate than the others.
(a) Voltage variation using 0.1M H2SO4 (b) Voltage variation using 0.2M H2SO4
(c) Voltage variation using 0.3M H2SO4 (d) Voltage variation using 0.4M H2SO4
(e) Voltage variation using all four constant currents

Fig.4-2 Comparison of voltage variation using various constant current in different HCl concentration
4.2.1.3 Comparing voltage variation with time in HCl and H2SO4 at (0.2 current)
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The voltage variation with different time intervals (30, 60, 120, 240, 360, 480, and 1440
mins) for hydrochloric acid (HCl) and sulfuric acid (H2SO4) at a constant current of (0.2) was
compared, as shown in the graph (Fig.4-3). As shown in Fig.4-3, the voltage variation with
time for scrap electrolysis in 0.4M of Hydrochloric acid (HCI) and sulfuric acid (H 2SO4)
solution increases steeply at first and then gradually over the next 24 hours.
However, because of the voltage flow's up-trill, the scrap at 0.2 for H 2SO4 has a lower
chance of passivation than the scrap at 0.2 HCl. When electrolyzed at 0.2 current in 0.4M
HC1, the selective dissolution of the Co binder from the scrap was efficient, and the voltage
in the H2SO4 system was lower than in the HCI system.
Fig.4-3 HCl and H2SO4 comparison in voltage variation at (0.2 current)
4.2.1.4 Selection of electrolyte and carbide scrap dissolution

Fig.4-4 depicts the variation of the characteristic current and dissolution of the scrap with
the concentration of Hydrochloric acid (HCl) and sulfuric acid H 2SO4 ranging from (0.1 M-
0.8M) at different voltages. As seen in Table 4-1 and 4-2, both the HCl current variation and
H2SO4 variation increased rapidly to a certain level and then decreased with increasing
concentration from 0.1 to 0.8 M, whereas the voltage curve decreased steadily. The
fluctuation of the HCl current was greater than that of H 2SO4. The smaller current variation of
HCl in dilute solution (< 0.8 M HCI) is due to acid depletion, whereas the smaller current
variation of HCl in concentrated solutions (> 0.1 M HCI), is due to the formation of insoluble
chlorides [102], which inhibit the cobalt dissolution. As a result, dissolution of the scraps in HCI
is better at 0.1-0.2 M, indicating an active-passive behavior. The plots in H 2SO4 also showed
the active-passive behavior. However, the corresponding characteristic current variation of
H2SO4 were much less in contrast to those in HCl. As a result, hydrochloric acid was more
effective than H2SO4 as an electrolyte for scrap electrolysis.
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HCl Concentration HCl current variation Voltage variation

0.1 0.189 0.1
Table 4-1 0.2 0.185 0.3 HCl
0.3 0.166 0.5
current 0.4 0.152 0.6 variation
with 0.5 0.117 0.75
0.6 0.075 0.8
0.7 0.061 1
0.8 0.026 1.25
concentration from (0.1 M-0.8M)
Table 4-2 H2SO4 current variation with concentration from (0.1 M-0.8M)
H2SO4 Concentration H2SO4 current variation Voltage variation
0.1 0.14 0.1
0.2 0.139 0.3
0.3 0.127 0.5
0.4 0.121 0.6
0.5 0.117 0.75
0.6 0.075 0.8
0.7 0.061 1
0.8 0.026 1.25
4.2.1.5 Tungsten Cobalt scrap XRD analysis

The surface component of the working electrode (tungsten carbide scrap) at the constant
current of 0.1 in 0.3 M of hydrochloric acid (HCl) and sulfuric acid (H 2SO4) solution and
the constant voltage of 1 with WC powder in 0.3 M of Hydrochloric acid (HCl) were
detected by X-ray diffraction (XRD). Fig.4-4 shows that the surface components were
exposed to insoluble tungsite acid mineral after being transitioned to WC. In the analysis,
Co was dissolved after tungsten mineral was formed, implying that the tungsite acid
mineral was the result of anodic passivation and anodic passivation was caused initially by
the limited diffusion of CO2+. When the voltage was lower, anodic oxidation was used to
dissolved Co continuously, leaving an inert WC layer that was gradually getting thicker.
The thickness of this layer increased continuously until the reaction interface was deep
第 42 页/共 51 页
enough and the Co was difficult to oxidize. The electrochemical processes were shown in
Fig.4-5. However, the electrochemical dissolution was controlled by internal diffusion.
Fig.4.4 X-ray diffraction patterns of working electrode (carbide scrap) surface (a) 24 h dissolved in 0.3 M
H2SO4 at 0.1 constant current, (b) 24 h dissolved in 0.3 M HCl at 0.1 constant current, (c) 24 h dissolved
in 0.3 M HCl at 1 voltage (WC powder)
(A)
l
(B)
△l
(C) WC
Co
HCl / H2SO4 solution
WO3H2O
Fig. 4-5 Working electrode schematic at (a) the continuous dissolution of Co, (b) the initial oxidation of
WC, (c) the WO3H2O film forming
第 43 页/共 51 页
4.3 Summary
This chapter investigated the variation of voltage with time utilizing different constant
current ranging from (0.05-0.2) in hydrochloric acid (HCl) and sulfuric acid (H 2SO4). The
comparison of both solution at the constant current of 0.2 were also analyzed. The main
conclusion are as followed:
1) Voltage with time for the scrap at 0.05 constant current in 0.1M HCl increase
steeply in the first 2-5 h from (1.59 V-1.80 V).
2) When the scrap was electrolyzed at 0.5 in 0.1M H 2SO4 solution, even in the absence
3) When both scraps electrolyzed in 0.4M of HCl and H2SO4 solution separately, the
acid mineral was the result of anodic passivation. When the voltage was lower, anodic
oxidation was used to dissolved Co continuously, leaving an inert WC layer that was
gradually getting thicker.
第 44 页/共 51 页
CHAPTER 5: CONCLUSION AND RECOMMENDATION
5.1 Conclusion
In this study, we investigated and analyzed the use of tungsten cobalt which contain the
composition (Wt%) of Co=6, and WC=94. We firstly conducted a set-up where the tungsten
cobalt was place in hydrochloric acid (HCl) and sulfuric acid (H 2SO4) solution and connected
to the power station that helps changes the constant current and constant voltage. Secondly,
we conducted an analysis on the current variation of cobalt scrap at different constant voltages
(CV), and thirdly, we also conducted an experimental analysis on the voltage variation of
cobalt scrap at different constant current (CC). The main conclusions of this study are as
follows:
1) When the time increases from (30-1440mins), there was a decrease in the variation
2) The high level of anodic current variation was achieved at the constant voltage of
1V for both solutions.
3) When both solution anodic current variation was compare at the constant voltage of
1, HCl still prove to be efficient for the scrap electrolysis process than H2SO4.
4) Voltage with time for the scrap at 0.05 constant current in 0.1M HCl increase
steeply in the first 2-5 h from (1.59 V-1.80 V). The magnitude of voltage flow for the scrap
electrolyzed at the current of 0.05 was lower than 0.1, 0.15, and 0.2, which cause the scraps at
0.05 to have high chance of passivation than the others.
5) When the scrap was electrolyzed at 0.5 in 0.1M H 2SO4 solution, even in the absence
6) When both scraps electrolyzed in 0.4M of HCl and H2SO4 solution separately, the
acid mineral was the result of anodic passivation.
第 45 页/共 51 页
5.2 Recommendation
(1) In this study, we investigated cemented cobalt scrap of anodic passivation in the
process of electrochemical dissolution and analysis of constant current and constant voltage
variation. It is recommended that other methods for the dissolution of anodic passivation be
selected and improved for further studies.
(2) The selection of other cobalt scrap with different composition should also be
compare and analysis on the dissolution and passivation process.
第 46 页/共 51 页
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ACKNOWLEDGEMENT
I would like to take this unique opportunity to thank and express my deepest gratitude to
God Almighty and every person who made this project possible in a direct or indirect way,
supporting me academically and socially during this scientific research. First of all, I would
like to thank Academician and Professor Chai Liyuan. I’m much honored to have three years
of study and life in your National Engineering Research Center for Heavy Metal Pollution
Prevention and Control research group. Thank you for building such a good platform for our
experimental research to be convenient.
I acknowledge and salute the big work and help of my supervisor Professor Zhongwei
Zhao and Professor Sun Fenglong. With your support and care, I have made the wisest choice
in the past three years of university. I admire your rigorous attitude and profound knowledge,
patient encouragement and advice you offered me and showing a good heart during the whole
period of my studies.
My thanks and appreciation also go to professor Chen Ai-liang for her immense help and
support during my big thesis. To my wonderful friend Varney Johnson, who never ceases to
support me and show me every necessary thing I need to do in order to accomplish my big
thesis, I am so grateful to have you around.
Last but not least, my immense gratitude goes to my lovely mom, my father, my
brothers, and all other family members and countrymates that supported me through prayers,
moral support, finance, and all kind of help. Finally, I would like to express my sincere thanks
to all teachers who participated in the review of this paper, and the experts who participated in
my thesis defense.
第 54 页/共 51 页

Naomie Kad Final Thesis

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本科毕业设计(论文)

指导教师： 赵中伟 孙丰龙

Research of anodic passivation in the process of electrochemical dissolution for

32 Figures，9 Tables， and 102 References

Keywords: Cemented carbide, Electrochemical dissolution, anodic passivation, recycling

CHAPTER 1: LITERATURE REVIEW....................................................................................

3.2.1 Constant Voltage analysis........................................................................................30

CHAPTER 1: LITERATURE REVIEW

1.1 General Overview

Tungsten is a steady transition metal with numerous applications including cemented

Antimony Germanium Platinum Group Metals

1.1.1.1 The importance of raw materials

summarized in Table 1-3.

1.1.2.2 Chemistry of Tungsten

Table 1-4 Reaction of tungsten metal with acids and alkalis

Global average dispersion output (%)

1.1.2.4 Tungsten applications

Dilute HCl :Co+ 2 HCl →Co Cl2 + H 2 (1-1)

1.1.3.3 Production of Cobalt

Fig.1-3 Pie chart of cobalt’s mine distribution by countries

1.1.3.4 Cobalt applications

Fig.1-4 Refined cobalt demand by end-use in 2015

1.1.4 Tungsten Carbide

reduction of W oxide to pure W and subsequent carbonation of W (minimum particle size:

Fig.1-5 Distribution of WC applications for different sectors

IV. High-temperature oxidation process

1.1.4.4 Sustainability of the tungsten carbide recycling industry

Anodic :2 H 2 O →O 2 ↑+4 H +¿+ 4 e ¿

1.2.2 W and Co recovery through EC process

powder to acid dissolution, followed by electromigration and electrodialysis to separate the

extremely difficult due to the different behavior of Co and W.

1.3 Research significance, Content, Innovation point and Technical Route

Figure 1-8 Research idea of the study

CHAPTER 2: MATERIALS AND METHODS

2.1 Experimental materials and methods

Sulfuric acid (H2SO4) GR Hengyang Kaixin Chemical Reagent Co., Ltd.

Hydrochloric acid (HCl) AR Sinopharm Chemical Reagent Co., Ltd.

pH meter control PH5-3E INESA Leici Co., Ltd

2.1.2 Cobalt scrab dissolution preparation (Set-up)

Fig.2-1 Cobalt scrap dissolution preparation process

2.1.3 Preparation of HCl and H2SO4

d. Constant Current: Voltage variation + HCl solution

CHAPTER 3: CURRENT VARIATION OF COBALT SCRAP

3.2 Results and discussion

3.2.1.1 Variation of anodic current with time in HCl solution

(e) Current variation using all four voltages

3.2.1.2 Anodic current variation with time in H2SO4 solution

(e) Current variation using all four constant voltages

Fig.3-3 HCl and H2SO4 comparison in current variation at (1V)

CHAPTER 4: VOLTAGE VARIATION OF COBALT SCRAP

(e) Voltage variation using all four voltages

4.2.1.2 Voltage variation with time in H2SO4 solution

(e) Voltage variation using all four constant currents

Fig.4-3 HCl and H2SO4 comparison in voltage variation at (0.2 current)

4.2.1.4 Selection of electrolyte and carbide scrap dissolution

HCl Concentration HCl current variation Voltage variation

4.2.1.5 Tungsten Cobalt scrap XRD analysis

CHAPTER 5: CONCLUSION AND RECOMMENDATION

[66] CISTERNAS L A, ORDÓÑEZ J I, JELDRES R I, et al. Toward the Implementation of Circular

[80] WEN D, FU R, LI Q. Removal of inorganic contaminants in soil by electrokinetic remediation

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指导教师：赵中伟孙丰龙