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Recovery and Concentration of Precious Metals From Strong Acidic Wastewater
Recovery and Concentration of Precious Metals From Strong Acidic Wastewater
1462 to 1470
#2011 The Japan Institute of Metals
Generally, trace precious metals remaining in wastewaters generated from the refining process of precious metals are not recovered, due to
a relatively high processing cost as well as various technical problems. Recovery of precious metals from wastewaters is very important for the
conservation of resources and the protection of environment. However, wastewaters containing a large amount of ammonium ion (NH4 þ ) cannot
be treated by general neutralization operation, due to formation of metal ammine complexes with increasing pH. In this study, the possibility of
recovering precious metals and other valuable metals from wastewaters by various traditional metallurgical processes such as cementation,
neutralization and reduction, were investigated. A recovery of 99% Copper (Cu), 96% Palladium (Pd), and 85% Gold (Au) by cementation using
Iron (Fe) powder, and 99.6% Cu, 99.5% Pd by cementation using Aluminum (Al) powder was achieved. However, complete recovery of all
valuable metals by a one-step cementation process was not possible. On the other hand, precious metals and other valuable metals including
Copper and Indium, etc., were precipitated by combining neutralization, deammoniation and reduction processes. Results showed that the
recovery of Platinum (Pt) in the reduction process was improved by adding deammoniation step. Finally, precious metals are concentrated in the
crude copper metal by fusion process. The recovery of Au, Ag, Pd was more than 91%, and that of Pt was about 71%.
[doi:10.2320/matertrans.M2010432]
(Received December 24, 2010; Accepted April 5, 2011; Published May 25, 2011)
Keywords: wastewater, precious metals, cementation, neutralization, deammoniation, reduction, fusion
Scrap Materials
Precipitate
dissolution Aqua regia
(AgCl)
Concentration/
HCl
Denitrification
Au-Recovery
Crude-Au Na2SO3
(Reduction)
Pt-Recovery H 2O 2
Crude-Pt (Precipitation)
(1) Discarded electronic parts (CPU, etc.) (K2PtCl6) KCl
Pd-Recovery NH3
Crude-Pd (Precipitation)
(PdCl2(NH3)2) HCl
Wastewater
Table 2 The composition of samples obtained for reduction experiments. Figure 3 shows recovery behavior of the different ele-
Precious metals concentration (mg/L) ments. Complete recovery of Cu was achieved within 3–6 h
Reduction conditions by using Fe and Al powders. Maximum recovery of Au was
Au Pt Pd
obtained in less than 30 min and did not change up to 6 h.
Deammoniation 4.2 15.3 136.8
Also, the recovery of Pd reached maximum (>90%) within
Non-deammoniation 5.8 12.9 131.5
1–3 h by using Fe and Al powders and remained constant up
to 6 h. Pt recovery was only about 20% during cementation
time of 6 h.
from neutralization at pH 6 was performed with the addition In general, it is difficult to recover indium by cementation
of NaOH and heating. This process is usually referred to as method because standard electrode potential of indium is
the ‘‘Ammonia stripping method’’.19) To evaluate efficiency lower than that of other elements such as precious metals.
of the reduction process, tests were performed both with and However, indium was recovered by using Zn powder, unlike
without deammoniation process and results obtained are Fe and Al powders. It was also found that the pH of solution
given in Table 2. increased during the cementation tests, depending upon
100 mL of wastewater sample (deammoniated or non- the type of the cementation agent being used. The initial pH
deammoniated) was put into a 300 mL beaker and was stirred of solution was 0.15. However, the pH of solutions at the
by using a magnetic stirrer. 3 mL of sodium borohydride end of cementation with Fe, Al and Zn increased to 1.2, 3.5
(2.6 mol/L-NaBH4 solution) was added while solution pH and 5.6, respectively. A final solution pH of 5.6 with Zn
was monitored using a pH-meter. After boiling the sample powder suggests that the recovery of indium in solution
for 15 min, it was removed from heater and left overnight, occurs as indium hydroxide precipitation due to increasing
followed by filtration under reduced pressure using a 5C pH.
filter paper. The filtrated water was properly diluted and When Zn powder was used as a cementation agent, pH of
prepared for analysis of each metallic ion in solution by ICP- the solution was greatly increased, compared to the case of
AES. using Fe and Al powder. More work is needed to clarify this
behavior. Due to the complex composition of wastewater,
2.3 Wastewater treatment by combining precipitation this reaction mechanism is still being investigated.
and fusion Results given in Fig. 3 indicate that the optimum cemen-
The recovery of precious metals and other valuable metals tation time is 6 h, due to the complete recovery of copper with
were investigated by combining precipitation and fusion high concentration (12,293 mg/L). At 6 h cementation time,
processes, where fusion was performed to decrease the the recovery of 99.5% Cu (Al power), 98.2% In (Zn powder),
volume of the precipitate.20) Precipitation method was 73.4% Au (Fe powder), 99.5% Pd (Al powder) and 24.9% Pt
selected from the results of preliminary cementation, neu- (Zn powder) were achieved.
tralization and reduction tests discussed above. 3.1.2 Effect of cementation agents
Starting wastewater solution sample for the combined The effect of different cementation agents; Fe, Al and Zn
precipitation and fusion tests was a 3,000 mL solution, details metal powders (added at 0.2 and 0.4 mol/L) on the recovery
provided in Table 1. The precipitate obtained from the of Cu, Au, In, Pd and Pt in the wastewater during cementation
optimum conditions was charged into a graphite melting pot tests performed for 6 h is shown in Fig. 4.
with 50 g of flux (borax) and heated in a high frequency With Fe metal powder addition, Cu recovery reached over
induction furnace under air atmosphere. The surface temper- 95% for 0.2 mol/L and over 99% when Fe concentration was
ature of fusion was measured by using an infrared radiation increased to 0.4 mol/L. Au recovery reached over 80% with
thermometer. The sample in the melting pot was taken out in 0.2 mol/L Fe addition but decreased slightly to 70% when Fe
a mold after maintaining temperature at 1300 to 1700 C for addition was increased to 0.4 mol/L. Pd recovery was also
30 min and then cooled rapidly. Metallic fraction and crushed very high above 90% for both Fe concentrations. However,
slag were dissolved using HNO3 solution or aqua regia, and indium and Pt recoveries were extremely low.
then these solutions were properly diluted. With Al metal powder additions, over 99% Cu was
Distributions of each element in the metal and slag recovered with Al concentration of 0.4 mol/L and reduced
fractions were finally determined from analysis of these by half when Al was reduced to 0.2 mol/L. Au recovery
solutions by using ICP-AES equipment. remained consistent at near 70% under both 0.2 and 0.4
mol/L Al addition. Pd recovery was extremely high at over
3. Results and Discussion 98% for Al addition at 0.2 mol/L and over 99% at Al addition
of 0.4 mol/L. Like in Fe metal powder addition, In and Pt
3.1 Cementation recovery was again very low at below 5 and 20% for the two
3.1.1 Effect of cementation time metals respectively.
The effect of cementation time on the recovery of Cu, In, Cementation with 0.4 mol/L Zn metal powder when
Au, Pd and Pt in the wastewater sample during addition of Fe, compared against Fe and Al metal powders, a very high
Al and Zn metal powders was investigated and results recovery of indium at over 99% was achieved. Recoveries
obtained are shown in Fig. 3. Mole ratio of the metal powders of other metals remained lower compared to Fe and Al
(cementation agents) to Cu content in the wastewater powders.
(cementation agent/Cu) was fixed at 2. (Cementation agent Pure Pt metal has high standard potential and can be
was added at 0.4 mol/L). recovered by cementation on the electro chemical principle.
Recovery and Concentration of Precious Metals from Strong Acidic Wastewater 1465
(1) Cu (2) In
100 100
90 90
80 80
Cu - recovery (%)
In - recovery (%)
70 70
60 60
50 Fe 50 Fe
40 40
Al Al
30 30
20 Zn 20 Zn
10 10
0 0
0 100 200 300 400 0 100 200 300 400
Reaction time, t /min Reaction time, t /min
(3) Au (4) Pd
100 100
90 90
80 80
Au - recovery (%)
Pd - recovery (%)
70 70 Fe
60 60 Al
50 50
Zn
40 40
Fe
30 30
20
Al 20
10 Zn 10
0 0
0 100 200 300 400 0 100 200 300 400
Reaction time, t /min Reaction time, t /min
(5) Pt
Pt - recovery (%)
50
40 Fe Al Zn
30
20
10
0
0 100 200 300 400
Reaction time, t /min
Fig. 3 Effect of type of cementing agent (Fe, Al and Zn) on recovery of various metals during cementation.
However, in this cementation test, the recovery of Pt was concentration (12,293 mg/L). Indium was recovered by
only about 20% and this might be due to formation of using Zn powder (added at 0.4 mol/L), unlike Fe and Al
complex ions, which has low standard electrode potential powder. Under the cementation conditions tested (0.2 and
making it difficult for cementation. In the cementation 0.4 mol/L Fe, Al, Zn powder addition, 6 h), the recovery of
condition with 0.4 mol/L Zn powder, the recovery ratio of Pt was only about 20%.
indium was more than 99%. This behavior might be due to
the increase of pH value (refer to section 3.1.1 Effect of 3.2 Neutralization by using NaOH
cementation time). Figure 5 shows recovery of metals dissolved in the
When 0.2 mol/L or 0.4 mol/L of Fe powder was added to wastewater at different pH conditions from pH 2 to pH 12
the wastewater, the recovery ratio of Cu, Au and Pd were (pH adjusted with NaOH). Complete indium recovery was
relatively high in both experimental conditions. Also, the achieved at pH 4 and Cu recovery reached over 95% between
highest recovery ratio of Au was achieved by using Fe pH 5 and 6 but decreased to below 10% when pH was further
powder as a cementation agent. Therefore, comparative increased to over pH 7. The recovery of Pd remained
tests of cementation agents confirmed usefulness of Fe constant at around 12% under all pH conditions. Au and Pt
powder. recoveries reached maximum at around pH 7 of 50% and
3.1.3 Summary of cementation 30% for the two metals respectively but decreased at higher
Results from cementation section showed that Cu, Au and pH conditions due to re-dissolution. Following are the factors
Pd can be recovered by using Fe and Al powder, but Fe that might influence the amount of re-dissolution. There are
powder was more effective in recovering of Au than Al large quantities of ammonium ions (NH4 þ ) in wastewater
powder. Also, the optimum addition amount of cementation used in this experiment. Therefore, NH4 þ becomes NH3 with
agent and cementation time is 0.4 mol/L and 6 h, respec- increasing pH. For example, Cu forms an ammonia complex
tively, due to the complete recovery of copper with high species and thus dissolves again.21)
1466 H. Umeda et al.
60 70 Au
50
40
60 Pd
30 50 Pt
20
10
40
0 30
Cu Au In Pd Pt
20
(2) Al-powder addition: 0.2mol/L 0.4mol/L 10
100
90 0
80
1 2 3 4 5 6 7 8 9 10 11 12 13
70
Recovery (%)
60 pH
50
40 Fig. 5 Behavior of each metallic element during neutralization by using
30 NaOH.
20
10
0
Cu Au In Pd Pt
(1) Fe-Cementation (2) Al-Cementation
(0.4 mol/L, 360 min) (0.4 mol/L, 360 min)
(3) Zn-powder addition: 0.2mol/L 0.4mol/L Cu
100 In
90
80 Au
Pd
70
Recovery (%)
Pt
60
50 0 20 40 60 80 100 0 20 40 60 80 100
40
Metal recovery (%) Metal recovery (%)
30
20
10
(3) Zn-Cementation (4) NaOH-Neutralization
0 (0.4 mol/L, 360 min) (pH: 6.0, 15 min)
Cu Au In Pd Pt
Cu
Fig. 4 Effect of type of metallic powder on recovery of various elements at In
the end of cementation.
Au
Pd
Pt
Recovery (%)
Recovery (%)
Pt
60 60
50 50
40 40
30 30
20 20
Au Pd Pt
10 10
0 0
1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 4 5 6 7 8 9 10 11 12 13
pH pH
Fig. 7 Effect of deammoniation on recovery of precious metals during reduction by using NaBH4 . (Reduction of filtrated water generated
from neutralization.)
Au Cu 5000 Cu
Pt Fe
Intensity (a.u.)
4000
Ag Pb
3000
Pd Bi
2000
0 20 40 60 80 100 0 20 40 60 80 100
1000
Recovery (%) Recovery (%)
0
(3) Other metals -2 (4) Other metals -3 20° 30° 40° 50° 60° 70° 80°
Ni Al 2θ
Cr In
<Exhaust gas>
0 20 40 60 80 100 0 20 40 60 80 100
Recovery (%) Recovery (%) <Concentrate (Crude copper)>
<Wastewater> Recovery
1st treatment (Neutralization) Au : 38.2 mg Processing Au : 36.5 mg 95.5 %
2nd treatment (Reduction) Pt : 58.5 mg Neutralization
Pt : 41.6 mg 71.1 %
(Deammoniation)
Fig. 9 The recovery ratio of various elements at the end of neutralization Ag : 36.5 mg Reduction Ag : 33.4 mg 91.5 %
(pH of solution: 6.0) and reduction processing (pH of solution: 7.5) in the Fusion
Pd : 555.1 mg Pd : 519.1 mg 93.5 %
wastewater treatment.
Table 3 Recovery of various metals and the composition (grade) of metal <Wastes>
obtained from fusion process.
Grade Content
(A) Precious Recovery < Slag> < Final wastewater>
metal Wastewater MetalÞ Wastewater MetalÞ (%)
(mass%) (mass%) (mg) (mg) Au : 0.99 mg 2.6 % Au : 0.72 mg 1.9 %
Au 0.0010 0.09 38.2 36.5 95.5 Ag : 0.98 mg 2.7 % Pt : 10.9 mg 18.7 %
Pt 0.0018 0.11 58.5 41.6 71.1
Ag 0.0010 0.09 36.5 33.4 91.5
Fig. 11 Experimental results of precious metals recovery from initial
Pd 0.0157 1.32 555.1 519.1 93.5 wastewater to the concentrate by wastewater treatment.
Grade Content
(B) Other Recovery
metal Wastewater MetalÞ Wastewater MetalÞ (%) 3.5.3 Material balance in the wastewater treatment
(mass%) (mass%) (g) (g)
Figure 11 shows the recovered amount of precious metals
Cu 1.029 80.1 38.11 31.43 82.5 (such as Au, Pt, Ag, Pd). In addition, the material balance of
Fe 0.021 0.78 0.70 0.31 43.8 this wastewater treatment is shown in Fig. 12. This experi-
Pb 0.010 0.20 0.37 0.08 21.0 ment was performed in air atmosphere, and maximum
Bi 0.026 1.66 0.87 0.65 75.3 melting temperature was 1700 C. As a result, the oxidation
Ni 0.056 4.69 1.90 1.84 96.6 and volatilization reaction occurred, and then, each metallic
Sn 0.011 0.68 0.33 0.27 80.5 element, unlike precious metals, was distributed to the slag
Cr 0.004 0.00 0.13 0.00 0.0 and the air. On the other hand, most of precious metals were
Al 0.015 0.00 0.50 0.00 0.0 distributed to the Cu-metal (concentrate).22)
Zn 0.394 1.08 13.19 0.42 3.2 The main purpose of this experiment was to recover
In 0.090 0.00 3.13 0.23 7.4 precious metals. Au, Ag, Pt, Pd were absorbed and recovered
Þ
Metal was obtained from fusion process. by a Cu-metal (concentrate). The recovery of Au, Ag, Pd was
more than 91%, whereas that of Pt was about 71%. On the
other hand, according to the preliminary test, when deam-
Table 3 shows both the recovery of various metals and the moniation of the wastewater was not performed, recovery of
composition (grade) of metal obtained from fusion process. Pt was about 20%. And about 70% of Pt remained in the
Also, Fig. 10 shows the X-ray diffraction pattern of metal wastewater. Therefore, it is thought that recovery of Pt rises
obtained from fusion. It can be seen that metal (concentrate) due to the deammoniation of the wastewater. Relation
obtained from this experiment contained mainly Cu and other between the reduction of Pt and the deammoniation are
precious metals. being investigated now.
Recovery and Concentration of Precious Metals from Strong Acidic Wastewater 1469
<Material Balance> < Recycling process > < Conventional Cu-smelting >
RONBUNSHU 27 (2001) pp. 367–372. 16) K. Inoue: J. MMIJ 123 (2007) 59–67.
7) K. Liu, A. Shibayama, T. Suzuki, W. T. Yen and T. Fujita: J. MMIJ 117 17) Y. Shimada, T. Niide, F. Kubota, N. Kamiya and M. Goto: KAGAKU
(2001) 221–225. KOGAKU RONBUNSHU 36 (2010) pp. 255–258.
8) S. Ardiwilaga, T. Wakamatsu and Y. Nakahiro: Resourc. Process. 41 18) Y. Nakahiro: Resourc. Process. 40 (1993) 161–165.
(1994) 65–71. 19) A. Watanabe: J. Surf. Finish. Soc. Japan 48 (1997) 257–260.
9) W. Zhike, C. Donghui and C. Liang: Miner. Eng. 20 (2007) 581–590. 20) Y. Hirai and Y. Sasaki: Japanese Patent Disclosure H19-92133.
10) K. Hirayama: Proc. MMIJ Fall Meeting (1990) Vol. U, pp. 5–8. 21) H. Sato, Y. Shike, K. Takahashi, H. Nakazawa and Y. Kudo: Proc.
11) S. Nishimura: FLOTATION 31 (1984) 274–286. MMIJ Annual Meeting, (2001) Vol. II, pp. 36–37.
12) A. Okuda, H. Sawai, S. Ichiishi and J. Shibata: J. MMIJ 116 (2000) 22) K. Yamaguchi, H. M. Henao, S. Ueda and K. Itagaki: Proc. MMIJ Fall
929–933. Meeting, (2005) Vol. CD, pp. 247–248.
13) J. Shibata: J. Surf. Finish. Soc. Japan 53 (2002) 641–646. 23) T. Kametani, S. Akagi, F. Sato and K. Toda: Japanese Patent
14) A. Shibayama: J. MMIJ 120 (2004) 406–411. Disclosure H20-31547.
15) Y. Konishi: J. Soc. Powder Technol. Japan 43 (2006) 515–521. 24) A. Toraiwa and Y. Abe: J. MMIJ 116 (2000) 482–492.