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A method for recycling tantalum from waste tantalum capacitors by chloride metallurgy Bo Niu, Zhenyang Chen, and Zhenming Xu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b01839 • Publication Date (Web): 21 Dec 2016 Downloaded from http://pubs.acs.org on December 28, 2016
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A method for recycling tantalum from waste tantalum capacitors by chloride
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metallurgy
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Bo Niu, Zhenyang Chen, Zhenming Xu*
4
School of Environmental Science and Engineering, Shanghai Jiao Tong University,
5
800 Dongchuan Road, Shanghai 200240, People’s Republic of China
6 7 8 9 10 11 12 13
Corresponding author: Zhenming Xu
14
E-mail:
[email protected] 15
Tel: +86 21 5474495
16
Fax: +86 21 5474495
17
School of Environmental Science and Engineering
18
Shanghai Jiao Tong University
19
800 Dongchuan Road, Shanghai 200240, People’s Republic of China
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ABSTRACT
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The demand for tantalum (Ta) is rapidly increasing due to the manufacture of Ta
25
capacitors (TCs) for electronic devices. With the increasing awareness of
26
environmental protection and conservation of rare metal Ta, recycling of Ta from
27
waste TCs (WTCs) is becoming a hot topic for current society. In this study, an
28
efficient and environment-friendly process for recycling Ta from WTCs by chloride
29
metallurgy (CM) is proposed. In the CM process, the non-toxic FeCl2 is chosen as the
30
chlorination agent. Thermodynamic analysis demonstrates that Ta can selectively
31
react with FeCl2, and the generated TaCl5 can be easily separated and then condensed
32
in the condensation zone. The recovery of Ta can reach 93.56% under the optimal
33
chlorination parameters as follows: heating temperature of 500 oC, FeCl2 addition
34
amount of 50%, holding time for 2 h, and particle size of Ta-rich powder less than
35
0.24 mm. Moreover, the kinetic mechanism is discussed, and the rate-controlling step
36
in the chlorination reaction of Ta is determined by mixed control. No hazardous gas
37
and liquid waste are produced during the whole process. Therefore, this study presents
38
an environment-friendly and promising method for the cyclic regeneration of the rare
39
metal Ta from WTCs.
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KEY WORDS: Waste tantalum capacitors; tantalum; chloride metallurgy; cyclic
41
regeneration;
42 43 44
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INTRODUCTION Tantalum (Ta) is a rare metal which is chiefly used to manufacture tantalum
47
capacitors (TCs) for electronic products. For example, a mobile phone (3G technology)
48
contains about 36, the motherboard of a notebook (2GHz) 22, a digital camcorder
49
about 13 of these capacitors.1 As the number of electronic products has undergone
50
rapid growth, the global TCs consumption had been raised from 10 billion pieces in
51
2001 to 30 billion pieces in 2013.2 The huge market demand for TCs resulted in
52
increasing tantalum (Ta) resource demand. Currently, the world annual production of
53
Ta is only about 2000 tons, and 42% of Ta consumption (777 t) is used for TCs.1 Due
54
to the strong demand for Ta in capacitor manufacturing, the price of capacitor- grade
55
Ta reached $585/kg in 2016. In addition, Ta and niobium (Nb) are almost always
56
paired together in nature. These metals are difficult to separate because of their similar
57
physical and chemical properties.3 Consequently, large amounts of energy and
58
chemical will be required during the Ta separation and purification processes. Owing
59
to the increasing environmental awareness, it is significant to balance the demand for
60
Ta resource and minimize the impact of Ta processing on the environment.
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The recycling of Ta is an effective approach to balance the demand for Ta
62
resource and increase resource efficiency in production.4 In fact, current estimate
63
shows that nearly 45 million tons of electronic wastes are generated globally per
64
year,5 and large quantities of waste TCs (WTCs) will be discarded accordingly. The
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WTCs contain about 45 wt% of Ta, which is free of Nb.6 Therefore, WTCs could be
66
considered as high quality Ta resource for recycling. However, the recycling Ta from
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WTCs is difficult due to the coexistence of Ta with several materials - a capacitor
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consists of a sintered Ta anode, MnO2 or polymer cathode, silver paste and graphite
69
cathode layer, terminals (Fe-Ni), and mold epoxy resin (containing SiO2 powder), as
70
shown in Figure 1. Thus far, several related research such as phase separation,4
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combustion,6,7 steam gasification with NaOH,8 and chemical treatment6,9 have been
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done to recover Ta from WTCs in laboratory scale. These methods have palpable
73
effects on Ta recovery, but some problems still exist in the recycling processes. For
74
instance, gas pollutants can be generated in the combustion process and liquid waste
75
will be produced during the chemical treatment. Moreover, the solvent cannot be
76
unlimited cycle used, but this is not mentioned in these papers. Ta anode Ta wire
Ta2O5
MnO2 or Polymer
Graphite Silver paste
Anode terminal
Mold epoxy resin
Cathode terminal
77 78
Figure 1. Schematic illustration of a TC.
79
Chloride metallurgy (CM) has been proved to be a quite promising technology to
80
extract many nonferrous metals from their ores and concentrates.10-12 In the
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chlorination process, valuable metals are converted to their corresponding chlorides
82
and then separated based on the difference in volatility between the metal chlorides.
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This process does not produce liquid waste and is suitable for industrial large-scale
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production. The chlorination agent has an important role in the CM process. There are
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some possible chlorination agents such as chlorine (Cl2), hydrogen chloride (HCl),
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carbon tetrachloride (CCl4), sodium chloride (NaCl), magnesium chloride (MgCl2)
87
and ferrous chloride (FeCl2) etc.10 The gaseous or liquid chlorination agents
88
(including Cl2, HCl and CCl4) are efficient, but the hazardous and corrosive of these
89
gaseous or liquid chlorination agents require reactors to be both gases tight and
90
corrosion resistant.12 The metal chloride salts are more environment-friendly, since the
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chlorination reaction of metals using the chloride salts will not generate waste gases
92
and the process has low demand to the apparatus. Some rare earth elements in NdFeB
93
magnet and the rare metal titanium in metal scrap have been successfully extracted
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using chloride salts (MgCl2 and FeCl2).13-15 To the best of our knowledge, however,
95
little research about recycling Ta from WTCs using chloride salts were carried out.
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In this study, an effective and environment-friendly CM process for recycling Ta
97
from WTCs was proposed. In the CM process, the non-toxic FeCl2 was chosen as the
98
chlorination agent. The effect of chlorination parameters (such as reaction temperature,
99
holding time, FeCl2 adding amount, etc) on the Ta recovery rate were systematically
100
investigated. In addition, the thermodynamics and kinetic of the chlorination process
101
were analyzed. This study provides a theoretical foundation for recycling Ta from
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WTCs and also puts forward an environment-friendly and efficient way for resource
103
utilization of WTCs.
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EXPERIMENTAL
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Materials. FeCl2 (99.5%, Aladdin) was chosen as the chlorinating agent, and
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argon (Ar, 99.99% purity) was used as the shielding gas. The WTCs used in this study
108
were provided by Yangzhou Ningda Noble Metal Co., Ltd. (China) and Shanghai Xin
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Jinqiao Environmental Protection Co., Ltd. (China). The major compositions of the
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WTCs are listed in Table 1. About 20 g of WTCs were heated to 600 oC under Ar to
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remove the organic materials such as the mold epoxy resin. During the pyrolysis
112
process, oil was gathered by a condenser, and gas was collected by a gas bag. The
113
schematic illustration of the pyrolysis equipment was shown in Figure S1 of
114
Supporting Information (SI). After pyrolysis treatment, Ni-Fe terminals were
115
separated by magnetic separation. Then, the residues were crushed and classified into
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fractions of < 0.24, 0.24 - 0.45, 0.45 - 0.6 and 0.6 - 0.8 mm, respectively. The content
117
of Ta in the Ta-rich powder is shown in Table 2. The Ta-rich powder was used in this
118
experiment.
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Apparatus. The chloride metallurgy (CM) experiments were conducted in the
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quartz tube furnace, as shown in Figure 2. The main body consisted of a body of
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furnace (chamber dimension is Φ 40 mm × 600 mm), a quartz tube reactor (Φ 35 mm
122
× 800 mm), a gas supply system, and a temperature controller. The middle part of the
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quartz tube is the heating zone and the two ends of the tube far away from the heating
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zone were condensation zones.
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128
Table1 Main composition of the WTCs used in this study. Composition
Ta
organics
SiO2
Ni
Fe
Ag
Content
35.99 ±
11.21 ±
44.78 ±
6.10 ±
1.40 ±
0.48 ±
(wt %)
0.40
0.15
0.51
0.08
0.03
0.03
Table 2 The content of Ta in different particle sized Ta-rich powders. Particle size (mm)
< 0.24
0.24 - 0.45
0.45 - 0.6
0.6 - 0.8
Content (wt %)
60.28 ± 0.57
50.32 ± 0.36
43.48 ± 0.45
39.16 ± 0.28
129
130 131
Figure 2. Schematic illustration of the quartz tube furnace.
132
Methods. In a typical run, Ta-rich particles and FeCl2 powder were blended well
133
with a certain mass ration in a quartz boat, and put into the quartz tube. Ar gas was
134
passed through the reactor with a flow rate of 300 ml/min. The samples were heated
135
from room temperature to the preset temperature. After reaction for a period of time,
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the samples were cooled to room temperature, and the residues were taken out to
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calculate the recovery rate. The recovery rate of Ta was calculated by the following
138
formula: 7 ACS Paragon Plus Environment
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R = M − M⁄M × 100%
(1)
Where, M0 and M are the initial and remaining amount of Ta, respectively.
141
Analysis. The content of metals in the raw material and the solid product were
142
analyzed by inductively coupled plasma-mass spectrometry (ICP-MS, Agilent 7500a,
143
Agilent Corporation, US). The content of SiO2 and organics in WTCs were examined
144
by X-ray Fluorescence Spectrometer (XRF-1800, Shimadzu, Japan) and combustion
145
method.16 The crystal structure of products was identified by X-ray diffraction (XRD,
146
D8 ADVANCE, BRUKER, Germany) with Cu Kα radiation. All the measurements
147
were repeated three times, and only the mean values were reported.
148 149
RESULTS AND DISCUSSION
150
Thermodynamic analysis. Prior to the experimental study, the reactions between
151
FeCl2 and components in Ta-rich particles are discussed from thermodynamic
152
viewpoints. Figure 3a shows the Gibbs free energy variation of the reactions at 100 -
153
800 oC (the thermodynamic data were calculated by HSC Chemistry 5.0). It is obvious
154
that Ta can selectively react with FeCl2 above 380 oC. However, the reactions between
155
FeCl2 and other components such as Ta2O5, SiO2 and Ag will not occur because of the
156
positive free energy values. It indicates that it is possible to extract Ta from the Ta-rich
157
powder through chemical reaction. The chemical reaction involved in the extraction
158
of Ta with FeCl2 is as follows:
159 160
2 + 5 , = 2 + 5
(2)
For chloride metallurgy (CM), selective chlorination reaction is prerequisite, and
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the separation of different metal chlorides is crucial. The separation of chlorides from
162
each other is achieved by utilizing their different vapor pressures at certain
163
temperature. The metal chloride with high vapor pressure and low boiling point can
164
be separated through distillation or sublimation from other chlorides, and then be
165
recovered through condensation at certain temperature.10 Figure 3b shows the vapor
166
pressure of TaCl5 and FeCl2 as a function of temperature. The vapor pressure
167
calculations are listed in Table S1 of Supporting Information (SI). As shown in Figure
168
3b, the vapor pressure of TaCl5 is substantially higher than that of FeCl2. Moreover,
169
the boiling points of TaCl5 and FeCl2 at standard atmospheric pressure are 234 oC and
170
1026 oC, respectively. It means that TaCl5 can be evaporated into the gas phase, while
171
the excess FeCl2 will remain in the residues, with the chlorination temperatures
172
between 380 - 1000 oC.
173
Based on above thermodynamic analysis, we can draw a conclusion that, when
174
the chlorination temperature is between 380 - 800 oC, only Ta in the Ta-rich powder
175
can react with FeCl2, and generate gas phase TaCl5. The generated TaCl5 can be easily
176
separated from the reactants and subsequently condensed in the condensation zone.
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800 Ta2O5(s)+5FeCl2(s,l)=2TaCl5(g)+5FeO(s)
(a)
600
∆G (kJ/mol)
400 SiO2(s)+2FeCl2(s,l)=SiCl4(g)+2FeO(s) 200 2Ag(s)+FeCl2(s,l)=2AgCl(s)+Fe(s) 0 2Ta(s)+5FeCl2(s,l)=2TaCl5(g)+5Fe(s)
-200 100
200
300
400
500
600
700
800
o
177
Temperature ( C) 5
10
(b)
4
10 Vapor pressure (Pa)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
FeCl2 TaCl5
3
10
2
10
1
10
0
10
0
200
400
600
800
1000
o
178
Temperature ( C)
179
Figure 3 (a) Gibbs free energy variations of the reactions between FeCl2 and Ta-rich
180
particles at 100-800 oC; (b) vapor pressure of TaCl5 and FeCl2 as a function of
181
temperature.17
182
Effect of reaction conditions on Ta recovery rate. Tantalum (Ta) is the target
183
element of this study. In order to obtain the maximum Ta recovery rate, the effects of
184
FeCl2 adding amount, chlorination temperature, holding time and particle size of
185
Ta-rich powder on the recovery rate of Ta were investigated.
186
Figure 4a shows the relationship between Ta recovery rate and FeCl2 adding
187
amount (temperature: 500 oC, holding time: 30 min, particle size of Ta-rich powder: 10 ACS Paragon Plus Environment
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less than 0.24 mm). The recovery rate of Ta increased from 70.36% to 90.84% with
189
increasing the FeCl2 adding amount from 40 wt% to 50 wt%. But, the recovery rate
190
began to decrease when further increasing the adding amount of FeCl2. This indicates
191
that the excessive FeCl2 could impede the chlorination process for Ta. Therefore,
192
adding 50 wt% of FeCl2 was sufficient for the chlorination reaction of Ta. 92
95
(b)
(a) 90
Recovery rate (%)
Recovery rate (%)
90
85
80
88
86
75 84
70
65
82
40
45
193
50
55
60
400
450
FeCl2 adding amount (wt%)
500
550
600
o
Temperature ( C)
94
100
(c)
(d) 80
Recovery rate (%)
93 Recovery rate (%)
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40
20
91
30
194
60
60
90
120
150
0
180
< 0.24
0.24~0.45
0.45~0.6
0.6~0.8
Particle size of Ta-rich powder (mm)
Holding time (min)
195
Figure 4. Effects of (a) FeCl2 addition amount, (b) temperature, (c) holding time and
196
(d) particle size of Ta-rich powder on the recovery of Ta.
197
The relationship between Ta recovery rate and chlorination temperature is shown
198
in Figure 4b (FeCl2 adding amount: 50 wt%, holding time: 30 min, particle size of
199
Ta-rich powder: less than 0.24 mm). It shows that the effect of temperature on the
200
recovery rate of Ta is significant. The recovery of Ta could reach to 83.78%, when the 11 ACS Paragon Plus Environment
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201
chlorination temperature was 400 oC. It suggests that Ta can be started to chlorinate
202
by FeCl2 at this temperature, which is in accord with the above thermodynamic
203
analysis (the temperature is above 380 oC). The highest recovery rate appeared at 500
204
o
205
indicates that excess temperatures will not facilitate the chlorination reaction of Ta.
206
Therefore, controlling the chlorination temperature is an essential condition for a
207
higher Ta recovery rate.
C, and then the recovery rate decreased with the increase of temperature, which
208
The relationship between Ta recovery rate and holding time is shown in Figure
209
4c (FeCl2 adding amount: 50 wt%, temperature: 500 oC, particle size of Ta-rich
210
powder: less than 0.24 mm), which shows that the recovery rate of Ta can reach up to
211
90.84% at 30 min. A higher recovery rate could be obtained at 120 min and the
212
recovery rate of Ta was 93.56%. Thus, holding time for Ta chlorination process was
213
considered as 120 min.
214
Figure 4d shows the relationship between Ta recovery rate and particle size of
215
Ta-rich powder (FeCl2 adding amount: 50 wt%, temperature: 500 oC, holding time:
216
120 min). The results suggested that the recovery rate of Ta increased with reducing
217
the particle size. When the particle size of the Ta-rich powder was less than 0.24 mm,
218
the optimized recovery rate of Ta could be obtained.
219
The above experiments show that the recovery rate of Ta can reach 93.56% at the
220
conditions of FeCl2 adding amount: 50 wt%, chlorination temperature: 500 oC,
221
holding time: 120 min and particle size of Ta-rich powder: less than 0.24 mm.
222
Therefore, these conditions were considered as the optimal chlorination parameters
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for Ta-rich powder.
224
Characterization of reaction product. After the best conditions were
225
confirmed, the product under optimal conditions was analyzed. Figure 5a shows the
226
image of the condensed product, which presents white deposits on the inner wall of
227
the quartz tube. The white deposits were scraped off (Figure 5b) and analyzed by
228
XRD. Figure 5c shows the XRD pattern of deposits (condensing product). As shown
229
in Figure 5c, the peaks corresponding to tantalum oxide instead of TaCl5 were
230
observed, since TaCl5 is prone to hydrolysis and transforms into oxides of tantalum
231
when exposed in the air. Actually, TaCl5 will be inevitably exposed to air during the
232
collection process and preparation of the XRD measurement sample. The formed
233
tantalum oxide will be favorable due to the properties of easy storage and usage. In
234
addition, no other phases were observed in Figure 5c, demonstrating that the tantalum
235
oxide had a high purity. The ICP-AES result indicated that the purity of tantalum
236
oxide was over 99%.
237 4500 4000
(a)
(c)
Tantalum Oxide: JCPDF (19-1299)
♣
3500 Intensity (Counts)
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(b)
3000
♣
2500 2000
♣
1500 ♣
1000
♣ ♣
500
♣
1cm
10
20
30
238 239
♣
♣
0 40
50
60
70
80
2 Theta (Degree)
Figure 5 (a) The image of the condensed product in one end of the quartz tube, (b)
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240
the image of deposits scraped from the quartz tube, and (c) XRD pattern of the
241
deposits.
242
Kinetic analysis. Many kinetic equations of the solid - solid reactions are
243
reported in the literatures.18,
244
determined by chemical reaction control, ash diffusion control and the mixed
245
control.20 To further understand the chlorination process, the kinetic equations were
246
used to determine the rate-controlling step. The mathematical formulas for the
247
chemical reaction control, ash diffusion control, and mixed control are investigated in
248
equations 3, 4 and 5, respectively.
249
19
Generally, the solid - solid reactions could be
1 − 1 − / = !
(3)
250
1 − 2 ⁄3 − 1 − / = !
(4)
251
= #! +
(5)
252 253
Where R is the recovery rate of Ta; K is the reaction rate constant; t is the chlorination time; and C is a constant.
254
The analysis results of the chlorination process are shown in Figure 6. The best
255
correlation of the experimental data for the chlorination process of Ta was obtained by
256
equation 5, which indicates that the kinetic model for the chlorination reaction of Ta
257
could be described as the mixed control (chemical reaction and ash diffusion controls).
258
The chlorination process can be explained as the follows. Firstly, Ta will react with
259
FeCl2 under certain temperature, and the chlorination reaction proceeded with time
260
prolonging. During the chlorination process, the reaction residues were also generated
261
and then formed an ash layer (mainly Fe, as shown in Figure S2 of SI). As the reaction
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262
progress, the reaction residues gradually increased, leading to the thickening of the
263
ash layer. The ash layer would provide a barrier of the reactions between Ta and FeCl2.
264
Meanwhile, the gaseous products TaCl5 penetrated through the ash layer and reactants
265
(Ta rich particle and FeCl2), which was facilitated to the chlorination reaction. When
266
Ta or FeCl2 was exhausted, the reaction is terminated. Therefore, the mixed control
267
could be considered as the chlorination rate-controlling step. For the higher recovery
268
of Ta, decreasing the particle size of reactants and increasing the contact area between
269
reactants can be beneficial to the reaction (Figure 4d). 0.220
0.60
(a)
0.215
(b)
0.59 2/3
0.210
1-2R/3-(1-R)
1/3
1-(1-R)
0.58
0.57 Equation y = a + b*x Adj. R-Square 0.85724
0.56
0.205 0.200 Equation
B
Intercept
B
Slope
4.31251E-4
Value
8.62166E-5
0.190
30
60
90
120
0.88926
0.195
0.55
270
y = a + b*x
Adj. R-Square
Value Standard Error 0.54289 0.00858
150
30
B
Intercept
B
Slope
60
Time (min)
90
Standard Error
0.18779
0.00364
2.10379E-4
3.65559E-5
120
150
Time (min)
94.0 93.5
(c)
93.0 R
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92.5 92.0 Equation
y = a + b*x
91.5
Adj. R-Squar
91.0
B
Intercept
84.6948
0.6414
B
Slope
1.81688
0.14592
0.97469 Value
90.5 3.2
271
3.6
4.0
4.4
Standard Error
4.8
5.2
lnt
272
Figure 6. Kinetic plots of (a) chemical reaction control, (b) ash diffusion control, and
273
(c) mixed control of the chlorination process for Ta at 500 oC.
274
Environmental comparison with other processes. As stated in the introduction,
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recycling Ta from WTCs is an effective approach to balance the demand for Ta
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resource for social and environmental need. Therefore, some research has been done
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to recycle Ta from WTCs. In the existing research, WTCs are most treated via
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pyrometallurgy (high-temperature combustion) and hydrometallurgy including many
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wet steps to extract Ta. However, gas pollutants and liquid waste will be inevitably
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generated during the combustion and chemical treatment. An overview of the
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comparison between the proposed route and other processes for WTCs recycling is
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given in Table 3. Therefore, the proposed CM technology in this study can be
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regarded as an environment-friendly and promising process for recycling Ta from
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WTCs due to its excellent environmental and economic benefits.
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CONCLUSIONS
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An efficient and environment-friendly chloride metallurgy (CM) process has
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been proposed for the recovery of tantalum (Ta) from waste tantalum capacitors
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(WTCs). Compared to other hazardous and corrosive chlorination agents (Cl2, HCl
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and CCl4), the non-toxic FeCl2 was chosen as the chlorination agent in this study.
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Thermodynamic analysis demonstrates that Ta can selectively react with FeCl2, and
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the generated TaCl5 can be easily separated and then condensed in the condensation
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zone. The recovery of Ta could reach to 93.56% under the optimal chlorination
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parameters as follows: heating temperature of 500 oC, FeCl2 addition amount of 50%,
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holding time for 2 h, and particle size of Ta-rich powder less than 0.24 mm. In
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addition, the kinetic mechanism is discussed, and the rate-controlling step in the
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chlorination reaction of Ta is determined by the mixed control (chemical reaction and
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ash layer diffusion controls). No hazardous gas and liquid waste are produced during
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the whole process. Therefore, this study presents an environment-friendly and
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promising technology for the cyclic regeneration of the rare metal Ta from WTCs.
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Table 3 Overview of comparison between the proposed route and other processes for
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WTCs recycling Method processing steps
CM treatment chlorination extraction
Pyrometallurgy
Hydrometallurgy
calcination
many wet processing steps
Ta recovery rate
> 90%
> 90%
> 90%
energy consumption
lower energy consumption than pyrometallurgy
high energy consumption
___
time consumption
high efficiency
high efficiency
long periods of time
chemical use
only FeCl2 consumed
___
large amount of mineral acid and oxalate organic solvent strong alkali
emissions
Pyrolysis oil and gas were collected and could be recycled as energy resources
gaseous pollutant
large amount wastewater and acid
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ASSOCIATED CONTENT
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Supporting Information
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The Supporting Information is available free of charge on the ACS Publications
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website. Schematic illustration of the pyrolysis equipment; XRD patterns for the
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residue after CM; Saturated vapor pressure calculation of TaCl5 and FeCl2.
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ACKNOWLEDGMENTS
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This work was supported by the National Natural Science Foundation of China
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(51534005).
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REFERENCES
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For Table of Contents Use Only
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A method for recycling tantalum from waste tantalum capacitors by chloride
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metallurgy
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Bo Niu, Zhenyang Chen, Zhenming Xu*
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Recycle WTCs
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1cm Tantalum oxide
380 CM
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Synopsis
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Recycling Ta from WTCs by chloride metallurgy can achieve the sustainable
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utilization of Ta resource and reduce the pollution.
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