Chemical Engineering & Processing: Process Intensification 161 (2021) 108293

Contents lists available at ScienceDirect

Chemical Engineering and Processing - Process

Intensification
journal homepage: www.elsevier.com/locate/cep

Research on the purification of germanium residue by

outfield enhancement
Haokai Di a, b, c, Qihao Gui a, b, c, Fangfang Yang a, b, c, Ming Liang a, b, c, Hanlin Zeng a, b, c,
Kun Yang a, b, c, *, Libo Zhang a, b, c, *
a
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan, 650093, China
b
Key Laboratory of Unconventional Metallurgy, Ministry of Education, Kunming, Yunnan, 650093, China
c
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming, Yunnan, 650093, China

A R T I C L E I N F O A B S T R A C T

Keywords: In this paper, a new technique on purifying germanium-tannins residue with assistance of ultrasonic was
Germanium investigated by univariate method, in which the main reaction factors such as H2SO4 concentration, solid-liquid
Purify ratio, pickling time, pickling temperature and ultrasonic power were discussed respectively. The results indicated
Ultrasonic-assisted pickling (UAP)
that, with the reaction conditions of H2SO4 concentration of 0.2 M, solid-liquid ratio of 300 g/L, pickling time of
Cavitation
30 min, pickling temperature of 40 ℃ in regular pickling, the removal efficiency of impurities were: Zn 84.43 %,
Concentrate
Fe 71.15 %, Mg 85.16 %, As 80.33 %, with the Ge content grade was 2.86 %, and germanium concentrate with
28.4 % Ge content was obtained after roasting; when ultrasonic power of 225 W was introduced into solution, the
removal efficiency of impurities were: Zn 88.57 %, Fe 88.28 %, Mg 89.14 %, As 89.27 %, with the Ge content
grade was 4.11 %, and germanium concentrate with 35.6 % Ge content was obtained after roasting. Ultrasonic
energy, contrasted with regular method, provides a superior consequence with less pickling time, lower H2SO4
concentration and lower pickling temperature. Those can be attributed to the cavitation effect of ultrasonic,
which can not only destroy the germanium residue package, increase the contact area of the solid-liquid reaction,
but break some chemical bonds and promote the process of impurities removal.

1. Introduction germanium [8–10]. However, many impurities are contained in

Germanium belongs to scattered metal, an extremely critical stra­
tegic resource, which is widely used in many fields including aerospace,
optical fiber communication, electronic devices, solar cells and
biomedicine, etc [1]. There is no independent germanium ore in nature.
All germanium products are produced as by-products of other metals,
while germanium production in China mainly comes from the Zinc
metallurgical processes [2–4]. At present, the technological process on
producing metal germanium from zinc oxide dust bearing germanium
mainly includes the following processes: the acid leaching of zinc oxide
dust; the precipitating of germanium with tannins; the acid pickling of
germanium-tannins residue; the roasting of germanium-tannins residue;
the chlorination distillation of germanium concentrate; the hydrolysis of
germanium tetrachloride; the reduction of the GeO2 by hydrogen and
the purification of germanium ingot. Hydrolyzable tannins are organic
compounds composed of polyhydroxy aromatic rings [5–7], which are
capable of forming chelates optionally with metal ions, especially
germanium-tannins residue besides germanium, such as Zn, S, Mg, Fe,
As, Ca Mn, Pb and so on [11,12]. The chlorination distilling process
would consume a large amount of hydrochloric acid if too many im­
purities exist in germanium-tannins residue, and which will reduce the
leaching rate of germanium. Besides, the excessive consumption of hy­
drochloric acid will make a large number of HCl escape, this makes it
difficult to condense GeCl4 steam. The distillation residue and waste acid
solution produced by this way are also difficult to retreat. Thus, the
pickling of germanium-tannins residue is particularly significant for
yielding high quality germanium concentrate.
Germanium residues are mainly leached by sulfuric acid in industry.
An enterprise in China found that leached by sulfuric acid can not only
reduce the content of arsenic and sulfur to the production index, but also
increase the Ge content by 4%~5% in germanium-tannins. After calci­
nating, the Ge content of germanium concentrate was as high as 24 %
~30 %, reaching the international six-level standards [13]. A smelting
company in Yunnan Province conducted a detailed investigation about

* Corresponding authors at: Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan, 650093, China.
E-mail addresses: truepsyche@sina.com (K. Yang), zhanglibopaper@126.com (L. Zhang).

https://doi.org/10.1016/j.cep.2020.108293
Received 22 September 2020; Received in revised form 4 December 2020; Accepted 22 December 2020
Available online 3 February 2021
0255-2701/© 2021 Elsevier B.V. All rights reserved.
H. Di et al. Chemical Engineering and Processing - Process Intensification 161 (2021) 108293

the leaching process of germanium-tannins, the requirements for

removing impurities of germanium-tannins can be satisfied as following
conditions: liquid-solid ratio of 3~5:1, leaching temperature of 50~70
℃, leaching time of 1~3 h, and 2~4 times leaching [14]. After roasting
the purified residue, germanium concentrate with 35 % Ge content was
obtained. Those production methods mentioned above can produce high
quality germanium concentrates. Studies showed that sulfuric acid can
be selected as the preferred leaching agent for germanium-tannins res­
idue picking. Considering the higher standards in protecting environ­
ment, it is of great significance to improve production efficiency on the
basis of simplifying production process and saving energy.
Frequencies above 18KHz are usually considered to be ultrasonic.
With the rapid development of society, ultrasonic is more widely and
frequently applied in all aspects of industrial technology [15]. Studies
showed that negative pressure can be produced by ultrasonic cavitation
in the liquid, which disturbs liquid and then produces a large number of
bubbles. Pressures at the site of cavitation bubbles implosion may
exceed 10,000 psi and temperatures may reach 10,000 ℉. Moreover,
ultrasonic cavitation in a liquid medium generates many physical and
chemical effects such as shear forces, microjets, microstreaming and Fig. 1. XRD spectra of germanium residue.
shockwaves, etc. Those characteristics of ultrasonic can be applied to
industrial manufacture for improving the leaching efficiency. Jiang et al.
[16] studied the recovery of cobalt and lithium from spent Li-ion bat­
teries using ultrasound-assisted leaching. Compared with conventional
method, the ultrasound-assisted leaching showed a higher leaching ef­
ficiency under the same experimental conditionals. Zhang et al. [17]
found that 700 W is the best ultrasonic power on the leaching of
germanium from roasted slag containing germanium. Under the opti­
mum condition, the recovery of germanium could reach up to 92.7 %,
which is higher than the leaching rate of Ge 88.35 % on regular leaching
conditions. In addition, the leaching time can be reduced by as much as
60 %.
In this paper, because the low quality of germanium concentrate
produced in industry, ultrasonic power was introduced to the germa­
nium residue pickling process for removing impurities more efficiently.
Moreover, the comparative study on regular pickling (RP) and
ultrasonic-assisted pickling (UAP) of germanium-tannins residue was
discussed. In order to obtain the optimum technological parameters of
germanium-tannins residue pickling, the main reaction factors on
removing impurities were analyzed specifically. Then the mechanism of Fig. 2. The infrared spectra of (a) raw materials and (b) industrial tannins.
UAP was analyzed. Research in this paper takes positive significance in
utilizing resource efficiently, reducing waste discharge and improving combined with Table 1, it can be seen that the primary inorganic phases
production efficiency. of the residue are ZnSO4, MgSO4, Fe2(SO4)3, FeSO4, Zn2GeO4,
Zn3(AsO4)2. The comparison of the infrared spectra between industrial
2. Experimental tannins and raw materials in Fig. 2, it indicates that the raw materials
used in the experiments containing tannin-based complexes, since both
2.1. Materials of them owns identical characteristic absorption peaks [8,18], in the
wavelength range of 1300 to 4000 cm− 1.
The raw material of germanium residue used in this experiment was
obtained after processes of zinc oxide dust leaching and then tannins
precipitating in a local plant of Yunnan, China. Its appearance shows 2.2. Experimental procedure
dark gray-black, moisture content is about 55 %. The specific compo­
sitions and content are shown in Table 1. The mass concentration of This experiment mainly consists of two parts: the pickling process of
individual components in raw material and pickling residue are calcu­ rough germanium residues and the roasting process of purified residues.
lated by elemental quantitative analysis. X-ray diffraction (XRD) anal­ The experiment flow chart and equipment diagram are respectively
ysis was conducted to characterize the component phases in Fig. 1. In shown in Figs. 3 and 4.
addition, fourier transform infrared (FTIR) of the raw materials is shown For pickling process, it was carried out in a 250 mL glass beaker
in Fig. 2. which was settled in a PF-101S magnetic stirrer with constant temper­
As shown in Table 1, the components of germanium-tannins residue ature water bath. Meanwhile, a certain power of ultrasonic was intro­
mainly include Zn, S, Mg, Ge, Fe, As, Ca, Mg and Pb. According to Fig. 1, duced into reaction system. The ultrasonic generator has a frequency of
20 kHz and a power range of 50~900 W. The concentration of H2SO4
Table 1 used in pickling process was 0~0.7 M, the pickling temperature was
Major chemical composition of germanium residue (mass fraction, %). 20~70 ℃, the pickling time was 10~60 min, the solid-liquid ratio was
Zn S MgO Ge Fe As CaO Mn Pb 200~900 g/L, the ultrasonic power was 90~315 W and the magnetic
mechanical stirring at 300 r/min.
14.27 9.46 3.31 1.34 1.22 0.82 0.41 0.38
For roasting process, the purified residues obtained by pickling
＜0.005

2
H. Di et al.
Fig. 3. The flow chart of this experiment.
process was carried out in muffle furnace. This procedure was proceeded
in temperature of 650 ℃ and reaction time of 5 h.
2.3. Calculation formula
The removal of impurities in germanium residue can be calculated
according to the following equation [19]:
w × 0.45m0 − w1 × m1
η= 0 × 100% (1)
w0 × 0.45m0
Where η is the removal efficiency of impurity, %; m0 and m1 represent
the initial mass of sample and mass of pickling residue, respectively, g;
ω0 and ω1 refer to the mass concentration of metal in the sample before
pickling and pickling residue, respectively, %. Just to be clear, the water
content of raw materials used in this experiment is 55 %.
Fig. 4. Ultrasonic-assisted pickling (UAP) equipment.
3
Chemical Engineering and Processing - Process Intensification 161 (2021) 108293
3. Results and discussion
3.1. Pickling process
3.1.1. Effect of H2SO4 concentration
The effect of H2SO4 concentration on impurities removal efficiency
under regular pickling was conducted at solid-liquid ratio of 300 g/L,
pickling time of 30 min, pickling temperature of 40 ℃, and stirring rate
of 300 r/min. The effect of H2SO4 concentration on impurities removal
efficiency under ultrasonic-assisted pickling was conducted at solid-
liquid ratio of 300 g/L, pickling time of 30 min, pickling temperature
of 40 ℃, ultrasonic power of 225 W. The results are shown in Fig. 5.
It can be seen from Fig. 5 that the removal efficiency of impurities in
germanium residue increases with the increasing of sulfuric acid con­
centration, and then tends to be stable gradually. When leached by
water (H2SO4 concentration of 0 M), for RP, the removal efficiency of
Zn, Fe, Mg and As were 79.86 %, 18.85 %, 77.51 % and 49.92 %,
respectively; while for UAP, the removal efficiency increased dramati­
cally to 87.89 %, 39.59 %, 87.81 % and 58.41 %. When leached by water
(no H2SO4), both Zn and Mg had better removal efficiency for RP,
because they are mainly as form of sulfate compounds in residue. Both
zinc sulfate and magnesium sulfate are water-soluble, thus can be
partially removed. When ultrasonic was introduced into solution, the
removal efficiency of Zn and Mg increased significantly. It can be
attributed to the mechanical effects caused by ultrasonic in the solution
such as micro jets and shock wave [16,20,21], which greatly promotes
the dissolution of zinc sulfate and magnesium sulfate in the aqueous.
When leached by water, the removal efficiency of Fe and As in raw
material was not significant for RP and UAP. This is because a lot of dust
pickling solution which contains H3AsO3 and multiple metal sulfates
was absorbed in germanium-tannins residue. A series of chemical re­
actions could happen in aqueous such as, (2) hydrolysis reaction and (3)
intermediate compounds formation reaction. It also can be seen from
Fig. 5 that when sulfuric acid was used instead of water as the pickling
agent, the removal efficiency of Fe and As significantly increased with
the increasing of sulfuric acid concentration. This is
Fe2(SO4)3+6H2O = 2Fe(OH)3+3H2SO4 (2)
3ZnSO4+2H3AsO3=Zn3(AsO3)2+3H2SO4 (3)
because the hydrolysis of ferric compounds and the formation of
arsenate intermediate compounds are inhibited with the increasing of
H+ concentration in the solution. In addition, the arsenate in residue will
form arsenic acid in accordance with Eq. (4) and (5) and was removed.
The dissolution of ZnSO4 and MgSO4 in the constant solution tends to be
saturated and cannot be further dissolved. Therefore, the removal effi­
ciency of Zn and Mg do not change significantly with the continuous
increasing of sulfuric acid concentration. However, because element
germanium exists in forms of complex Ge-Tannins and
Zn3(AsO4)2 + 3H2SO4 = 3ZnSO4 + 2H3AsO4 (4)
H3AsO3 + H2SO4 = H3AsO4 + H2SO3 (5)
Zn2GeO4 in residue. Both of them are slightly soluble in sulfuric so­
lution, which cause the increasing loss of germanium with the increasing
H. Di et al.
Fig. 5. Effect of H2SO4 concentration on impurities removal efficiency under (a) RP and (b) UAP.
of sulfuric acid concentration, as shown in reactions (6) and (7). Thus,
the concentration of sulfuric acid in solution should not be chosen too
high, that could avoid excessive germanium loss in raw materials.
Zn2GeO4 + 4H2SO4 = 2ZnSO4 + Ge(SO4)2 + 4H2O
(GeTA) 2+ +
+ 2H = Ge 4+
+ 2HTA, TA represents the tannins molecules (7)
When compared with RP in sulfuric acid concentration of 0.2 M, UAP
shows obvious advantages in impurities removal efficiency: Zn
increased from 84.43% to 88.57%, Fe increased from 71.15% to
88.28%, Mg increased from 85.16% to 89.14% and As increased from
80.33% to 89.27%. It also can be seen that impurities removal efficiency
in UAP residue obtained at H2SO4 concentration of 0.2 M was better
than that in RP residue at 0.5 M. Then, the removal efficiency of im­
purities only slightly changed subsequently with the increasing of sul­
furic acid concentration. That is because the pickling process is mainly
controlled by the bulk diffusion at lower H2SO4 concentration [16], and
ultrasound can enhance the diffusion process obviously [21]. When
concentration of H2SO4 is over 0.2 M for UAP process and 0.5 M for RP
process, the reaction rate is fast enough and sufficient, thus the removal
efficiency of metal impurities no longer change with the increase of
H2SO4 concentration. Therefore, 0.5 M and 0.2 M of H2SO4 can be
chosen as the optimal concentration for regular and ultrasonic-assisted
pickling respectively in all subsequent experiments.
3.1.2. Effect of solid-liquid ratio
The effect of solid-liquid ratio on impurities removal efficiency under
RP was conducted at H2SO4 concentration of 0.5 M, pickling time of
Fig. 6. Effect of solid-liquid ratio on impurities removal efficiency under (a) RP and (b) UAP.
Chemical Engineering and Processing - Process Intensification 161 (2021) 108293
30 min, pickling temperature of 40 ℃, and stirring rate of 300 r/min.
The effect of solid-liquid ratio on impurities removal efficiency under
UAP was conducted at H2SO4 concentration 0.2 M, pickling time of
30 min, pickling temperature of 40 ℃, ultrasonic power of 225 W. The
(6) results are shown in Fig. 6.
As can be seen from Fig. 6, for both RP and UAP, the removal effi­
ciency of impurities increased with the decreasing of solid-liquid ratio, it
is due to the decrease of mixture viscosity and then reduce the diffusion
resistance [22]. In the solid-liquid ratio of 700 g/L, UAP is significantly
better than RP in removing Fe, Mg and As, with Fe increasing from
68.13% to 73.85%, Mg from 73.05% to 80.27% and As from 58.06% to
61.71%. However, the removal efficiency of Zn did not change appar­
ently compared with RP. Because the content of Zn2+ in solution has
been oversaturated, even the introduction of ultrasonic energy could not
promote the better dissolution of Zn2+ in the pickling solvent. For RP
and UAP, the removal efficiency of impurity will not change obviously
when the solid-liquid ratio is less than 300 g/L. The impurity ions
removal efficiency were lower at higher solid-liquid ratio, which may be
ascribed to the increase viscosity of mixture, the higher resistance of
mass transfer diffusion and the lack of sulfur acid [16,22]. Therefore, it
is reasonable to set 300 g/L as the preferred solid-liquid ratio for RP and
UAP in the subsequent experiments.
3.1.3. Effect of pickling time
The effect of pickling time on impurities removal efficiency under RP
was conducted at H2SO4 concentration of 0.5 M, solid-liquid ratio of
300 g/L, pickling temperature of 40 ℃, and stirring rate of 300 r/min.
4
H. Di et al.
The effect of pickling time on impurities removal efficiency under UAP
was conducted at H2SO4 concentration of 0.2 M, solid-liquid ratio of
300 g/L, pickling temperature of 40 ℃, ultrasonic power of 225 W. The
results are shown in Fig. 7.
In Fig. 7, compared with RP, when UAP at pickling time of 10 min,
the removal efficiency of Zn increased from 82.88 % to 85.53 %, Fe
increased from 75.78 % to 77.00 %, Mg increased from 83.95 % to 86.33
% and As increased from 77.19% to 85.40%. The reason why the
introduction of ultrasonic in solution can improve the removal efficiency
of impurities is that ultrasound can weaken the chemical reaction
boundary layer and promote the mass transfer of solid-liquid reaction
[16,17,23]. For both RP and UAP, the removal efficiency of As increased
first and then decreased with the increasing of reaction time. It is
because tannins molecules in solution have a strong binding force with
the high valence metal ions [24]. With the extension of reaction time,
As5+ in solution was adsorbed by tannins molecules again and remained
in the residue. Within the pickling time of 40 min for RP, the removal
efficiency of Zn, Fe, and Mg increased with the increasing of pickling
time, but almost kept invariable after 40 min. And UAP showed the
similar changes at 30 min as well. Thus, RP time of 40 min and UAP time
of 30 min were considered as the appropriate pickling conditions for the
subsequent experiments.
3.1.4. Effect of pickling temperature
The effect of pickling temperature on impurities removal efficiency
under RP was conducted at H2SO4 concentration of 0.5 M, solid-liquid
ratio of 300 g/L, pickling time of 40 min, and stirring rate of 300 r/
min. The effect of pickling temperature on impurities removal efficiency
under UAP was conducted at H2SO4 concentration of 0.2 M, solid-liquid
ratio of 300 g/L, pickling time of 30 min, ultrasonic power of 225 W. The
results are shown in Fig. 8.
Fig. 8 shows that temperature increasing in a limited extent will
promote the removal of impurities in residue. This is due to cavitation of
ultrasound increased in solution with the increasing of temperature,
which can also accelarate the reaction and diffusion rate of reactants
[25]. But when the temperature exceeded 50 ℃ for RP and 40 ℃ for
UAP, the removal efficiency of Zn, Fe and Mg tended to be stable, and As
declined sharply. The reason for this phenomenon is that the ultrasonic
cavitation is particularly sensitive to solution temperature. The vapor
pressure in the air bubble increased when temperature was high enough,
which made cavitation bubbles difficult to form and then took adverse
effects on cavitation intensity [26–28].
3.1.5. Effect of ultrasonic power
The effect of ultrasonic power on impurities removal was conducted
at H2SO4 concentration of 0.2 M, solid-liquid ratio of 300 g/L, pickling
time of 30 min, and pickling temperature of 40 ℃. Ultrasonic power was
Fig. 7. Effect of pickling time on impurities removal efficiency under (a) RP and (b) UAP.
5
Chemical Engineering and Processing - Process Intensification 161 (2021) 108293
adjusted in the range of 90~315 W. The results are shown in Fig. 9.
Fig. 9 indicates that the removal efficiency of impurities in germa­
nium residue presented a trend of increasing first but decreasing then
within ultrasonic power adjusting from 90 to 315 W; and the best con­
dition of ultrasonic power was obtained at 225 W. The main reason was
that the higher of ultrasonic power, the more cavitation bubbles
occurred near the particle surface [29], which can reduce the thickness
of diffusion layer and enlarge the reaction surface area of particles [21].
Furthermore, the smaller particle size will increase the contact area of
the solid-liquid reaction and make the reaction happen more easier [30].
The average particle size of filter residues at different ultrasonic power
are shown in Fig. 10. Compared with 90 W, the removal efficiency of Zn
and Fe decreased at ultrasonic power of 135 W. Because the residue
particle size increased at power of 135 W, which led to a decrease
contact area of the liquid-solid reaction system, and then hindering the
chemical reaction [22,23,31]. However, with the increase of ultrasonic
power continuously, the removal efficiency of impurities in germanium
residue began to decrease sharply. This because the cavitation effect in
solution is "saturated" at a higher power [17]. A large number of tiny
cavitation bubbles gather around solid reactant surface, some of them
escape from the solution before they can grow and burst [32], which
interfered with the introduction of ultrasound into the liquid. Therefore,
225 W was selected as the optimal power for UAP.
After a series of conditional experiments, the best procedure gained
under ultrasonic filed is H2SO4 concentration of 0.2 M, solid-liquid ratio
of 300 g/L, pickling time of 30 min, pickling temperature of 40 ℃ and
ultrasonic power of 225 W, the Ge content grade of pickled residue is
4.11 %; while the Ge content grade of residue obtained in RP is 2.86 %.
3.2. Comparison of RP and UAP residues
For RP and UAP residues, the analysis of SEM, Mastersizer particle
size and X-ray diffraction were carried out separately to analyze the
differences between them. The SEM images of RP residues and UAP
residues are shown in Fig. 11. According to Fig. 11 (a) and (b) at the
same magnification of 1000 x, the UAP residue possesses the finer par­
ticles and an dispersed distribution in the filed of view. As can be seen
from Fig. 11 (c) and (d) at the same magnification of 8000 x, when
pickling with regular method, the encapsulated particles were not
crushed effectively, which resulted in the reduction of impurities
removal efficiency. Images of UAP residue showed many small holes and
cracks upon its surface, which led to the reduction of agglomeration.
Fig. 12 shows different particle size distributions of final filter residues
by RP and UAP. It can be seen from Fig. 12 that the particle size of UAP
residue has a broad distribution in the smaller particle diameter area. At
this point, the median particle size of the filter residue is
D50 = 31.768 μm, which is more smaller than 67.698 μm obtained by RP.
H. Di et al.
Fig. 8. Effect of pickling temperature on impurities removal efficiency under (a) RP and (b) UAP.
Fig. 9. Effect of ultrasonic power on impurities removal efficiency: H2SO4
concentration = 0.2 M, solid-liquid ratio = 300 g/L, pickling time = 30 min,
pickling temperature = 40 ℃..
Fig. 10. The average particle size of filter residues at different ultra­
sonic power.
Fig. 13 is the XRD patterns of raw materials, RP residues and UAP
residues. It can be seen from Fig. 13 that the XRD peak intensity of
impurity components in UAP residue is weak, which indicates that the
inorganic components are removed more thoroughly. Additionally,
Fig. 13 also shows that those heterogenous peaks appear in the same
6
Chemical Engineering and Processing - Process Intensification 161 (2021) 108293
position no matter for RP residues or UAP residues. It indicates that the
introduction of ultrasound into reaction system can not creat new phase
[16].
3.3. Mechanism of UAP
The method about pickling raw materials with sulfuric acid can
remove metal impurities because of the difference in the stability of the
complex formed by hydrolyzable tannins and different metal ions [24,
33]. By adjusting the pH of the reaction system in an appropriate range,
the impurity metal complexes can not only be dissociated and dissolved
into the solution, but also the target metal (Germanium) can remain in
the residue as much as possible, so as to achieve the purpose of impurity
removal.
Fig. 14 is the Fourier transform infrared spectroscopy (FTIR) spectra
of industry tannins, raw materials and UAP residues. It can be seen from
FTIR that UAP residue varies from raw materials in many aspects: the
wide peak between 3100− 3500 cm− 1 is related to OH stretching vi­
brations of phenolic in tannic acid structure [33–36], the peak of OH
shifted to 3439 cm-− 1 from 3404 cm-1 and the strength became stronger;
peak 1713 cm− 1 is the carbonyl C– – O stretching [37], which was weak
in raw materials; the peaks at 1625 cm− 1 moved to 1615 cm− 1, peaks of
1497 cm-1 and1445 cm− 1 became stronger which can be attributed to
C–– C of aromatic [33,38,39]; compared with raw materials, the asym­
metrical stretching peaks C–O at 1356 cm-1 and 1204 cm-1 [36,40],
became wider and stronger; peak of C–O–C stretching shifted to
1068 cm-1 from 1144 cm-1, which was too weak to be detected in cor­
responding position for UAP residue; peaks at 870 cm− 1 and 760 cm− 1
belonged to C–H out-of plane deformation [34,36,39,40]. These changes
can be attributed to the destructive effect of ultrasonic cavitation on
chemical bonds [41,42], and the impurity metal ions in complex that
combined with phenolic hydroxyl groups are replaced by H+ in the so­
lution, increasing the free hydroxyl groups in the system. Thus, the
pickling process can be regarded as the result of competition between a
large number of hydrion and metal impurity ions bound on phenolic
hydroxyl of tannin molecule in acid system [33].
UAP increases the removal efficiency of impurities, which can be
attributed to the cavitation in solution. The possible mechanism of UAP
in solution can be described as Fig. 15. When ultrasound is introduced
into the solution, millions of tiny bubbles generate in the solution, and
then vibrate, grow, and accumulate energy in the negative pressure
region. Those bubbles "collapse" sharply when the energy reaches a
certain threshold, causing a violent disturbance in the solution. The
explosion of those violent bubbles will generate enormous energy,
which will trigger a series of complex physical and chemical changes in
solution [43]. This powerful energy can destroy the germanium-tannins
residue package, expose impurity components to the leaching medium
H. Di et al. Chemical Engineering and Processing - Process Intensification 161 (2021) 108293

Fig. 11. SEM images of RP residues (a) and (c), UAP residues (b) and (d).

Fig. 12. Different particle size distributions of final filter residues by RP

and UAP..

Fig. 14. FTIR spectra of industry tannins, raw materials and UAP residues.

and promote the dissolution of impurity metal compounds Additionally,

Fig. 13. XRD patterns of raw materials, RP residues and UAP residues.
the powerful energy could also increase the contact area of the
solid-liquid reaction, enhance the mass transfer and accelerate the
chemical reaction process in solution. Furthermore, the ultrasonic
power could accelerate the fracture of metal-tannins complex bonds,
promote the removal of impurities in residues [44].
The order in which the metal impurities are removed is related to the
stability of the complexes. The greater the stability constant Kf of the
complex, the less likely it is to dissociate, and the greater its stability.
Liang et al. [24] studied the binding ability of different metal ions with
tannins in poly-metal solution. Experimental results show that metal
ions with relatively high valence and big ionic radius bind strongly to
tannins. Therefore, the removing order of metal impurities in the form of
complex may be: Zn＞Fe＞Mg＞As. In addition, due to the high solu­
bility of zinc sulfate and magnesium sulfate in the reaction system, the
dissolution rate is faster than that of Fe and As in the initial stage of the
reaction.

7
H. Di et al. Chemical Engineering and Processing - Process Intensification 161 (2021) 108293

Fig. 15. Mechanism of UAP of germanium residue.

3.4. Roasting process

Thermogravimetric analysis was conducted to compare the weight

loss and thermochemical behavior of Raw materials, RP residues and
UAP residues, which were studied in temperature region from 30 ℃ up
to 800 ℃ at a heating rate of 10 K/min with air atmosphere. The TG/
DSC curves were illustrated in Fig. 16.
Many researches [36,37,45] have been reported to analyze the
thermal stability of tannin-metal complexes. Combined with Fig. 16, it
can be seen that the weight loss process include three stages: the first
stage (30 ~ 165 ℃) is mainly the evaporation of water and the removal
of crystal water from the material. The second stage (165 ~ 285 ℃) is
the decarboxylation of the gallate acyl group in outer layer of organics.
The third stage (285 ~ 510 ℃) is the main stage of weight loss in the
thermal degradation process, which accounts for 63.99 % of the weight
loss in materials, mainly including the degradation of the gallate acyl
group in the inner layer of organics, the central glucose structure and the
oxidative decomposition of sulfide and arsenide. It also showed that the
residual amount roasted by unpickled raw materials is 41.13 %, and the
Ge content grade of purified residue is only 2.81 %, which completely
fails to meet the standards of chlorination distillation. The residual
Fig. 16. Thermogravimetric analysis of Raw materials, PR residues and
amount roasted by UAP residues accounted for 9.60 %, which was lower UAP residues.
than the RP residues. It indicates that the introduction of ultrasound
wave in solutions can remove impurities which are not easy to be
particles makes the reaction happen more easier, which enables the
removed by RP method, making it possible to obtain higher quality
removal efficiency of impurities in germanium residue more superior.
germanium concentrate. Experimental results about roasting purified
The results in this paper proposed a potential industrial method for the
residues showed that the Ge content of germanium concentrate was 28.4
purification of germanium-tannins residue.
% roasted by RP residue and 35.6 % roasted by UAP residue. The
pickling process of germanium-tannins residue by assistance of ultra­
CRediT authorship contribution statement
sonic can produce high quality germanium concentrate, which will not
only reduce the consumption of hydrochloric acid in the subsequent
Haokai Di: Conceptualization, Methodology, Validation, Formal
chlorination distillation process, but also greatly reduce the distillation
analysis, Investigation, Writing - original draft, Writing - original draft,
residue and acid waste liquid [46,47]. It is of great practical significance
Visualization. Qihao Gui: Methodology, Formal analysis, Investigation,
to make full use of resources, save production cost and protect
Writing - original draft, Writing - original draft, Visualization. Fangfang
environment.
Yang: Conceptualization, Writing - original draft, Visualization. Ming
Liang: Conceptualization, Methodology, Validation, Resources, Writing
4. Conclusions
- original draft, Visualization, Supervision. Hanlin Zeng: Conceptuali­
zation, Methodology, Resources, Supervision, Project administration,
For UAP process of germanium residue, the removal efficiency of
Funding acquisition. Kun Yang: Conceptualization, Methodology, Re­
impurities under optimal conditions are: Zn 88.57 %, Fe 88.28 %, Mg
sources, Supervision, Project administration, Funding acquisition. Libo
89.14 %, As 89.27 % respectively, with the Ge content grade is 4.11 %,
Zhang: Conceptualization, Methodology, Resources, Supervision, Proj­
and germanium concentrate with 35.6 % Ge content was obtained after
ect administration, Funding acquisition.
roasting. For RP process of germanium residue, the removal efficiency of
impurities under same conditions are: Zn 84.43 %, Fe 71.15 %, Mg 85.16
%, As 80.33 %, with the Ge content grade is 2.86 %, and germanium Declaration of Competing Interest
concentrate with 28.4 % Ge content was obtained after roasting.
When contrasted with RP, the application of ultrasonic makes it a The authors declare that they have no known competing financial
reality that the removal efficiency achieves more higher at less pickling interests or personal relationships that could have appeared to influence
time, lower H2SO4 concentration, lower pickling temperature. The the work reported in this paper.
higher quality germanium concentrate can be obtained by roasting UAP
residues. Those can be attributed to the ultrasonic cavitation, the Acknowledgements
enormous energy generated by cavitation in solution can smash the raw
materials, and reduce the particle size to a smaller level. The smaller size This work was supported by National Natural Science Foundation of
China [grant number 51974141], High-level Talent Discipline

8
H. Di et al.
Construction Funding of Kunming University of Science and Technology
[grant number 130214119521], and Analysis and Testing Foundation of
Kunming University of Science and Technology [2019M20182202075].
References
[1] J. Wang, A. He, Modern Germanium Metallurgy, Metallurgical Industry Press,
Beijing, 2005.
[2] R. Moskalyk, Review of germanium processing worldwide, Miner. Eng. 17 (2004)
393–402.
[3] F. Liu, Z. Liu, Y. Li, Z. Liu, Q. Li, L. Zeng, Extraction of gallium and germanium
from zinc refinery residues by pressure acid leaching, Hydrometallurgy 164 (2016)
313–320.
[4] R. Höll, M. Kling, E. Schroll, Metallogenesis of germanium—a review, Ore Geol.
Rev. 30 (2007) 145–180.
[5] D.S. Seigler, Phytochemistry of Acacia—sensu lato, Biochem. Syst. Ecol. 31 (2003)
845–873.
[6] J. Rutledge, C. Anderson, Tannins in mineral processing and extractive metallurgy,
Metals 5 (2015) 1520–1542.
[7] O. Gonultas, M.B. Ucar, Chemical composition of some commercial tannins
produced in Turkey, in: Proceedings of the 55th International Convention of
Society of Wood Science and Technology, Beijing, China: Society of Wood Science
and Technology, 2012.
[8] M. Kul, Y. Topkaya, Recovery of germanium and other valuable metals from zinc
plant residues, Hydrometallurgy 92 (2008) 87–94.
[9] M. Gurung, B.B. Adhikari, H. Kawakita, K. Ohto, K. Inoue, S. Alam, Recovery of
gold and silver from spent mobile phones by means of acidothiourea leaching
followed by adsorption using biosorbent prepared from persimmon tannin,
Hydrometallurgy 133 (2013) 84–93.
[10] M. Gurung, B.B. Adhikari, S. Alam, H. Kawakita, K. Ohto, K. Inoue, Persimmon
tannin-based new sorption material for resource recycling and recovery of precious
metals, Chem. Eng. J. 228 (2013) 405–414.
[11] B. Zhang, J. Wang, Y. Peng, K. Xu, Comprehensive recovery of indium and
germanium in zinc hydrometallurgy process, Yunnan Metallurgy (2007).
[12] Y. Huang, F. Xie, Study on measure of reducing sulfur content in germanium
concentrate and improving its grade, Yunnan Metallurgy (2002).
[13] B. Xu, Technical discussion on preparation of high grade germanium concentrate
from tannic germanium by acid cleaning, China Metal Bulletin 19 (2003) 19–22.
[14] D. Yang, Y. Li, H. Zhang, W. Yang, L. Dai, A method for preparing high grade
germanium concentrate from germanium containing leaching solution, China：
108486360 A, 2018-09-04.
[15] T.J. Mason, Ultrasonic cleaning: an historical perspective, Ultrason. Sonochem. 29
(2016) 519–523.
[16] F. Jiang, Y. Chen, S. Ju, Q. Zhu, L. Zhang, J. Peng, X. Wang, J.D. Miller,
Ultrasound-assisted leaching of cobalt and lithium from spent lithium-ion batteries,
Ultrason. Sonochem. 48 (2018) 88–95.
[17] L. Zhang, W. Guo, J. Peng, J. Li, G. Lin, X. Yu, Comparison of ultrasonic-assisted
and regular leaching of germanium from by-product of zinc metallurgy, Ultrason.
Sonochem. 31 (2016) 143–149.
[18] A. Ricci, K.J. Olejar, G.P. Parpinello, P.A. Kilmartin, A. Versari, Application of
Fourier transform infrared (FTIR) spectroscopy in the characterization of tannins,
Appl. Spectrosc. Rev. 50 (2015) 407–442.
[19] F. Zhang, Accurate Calculation of Leaching Rate, Nonferrous Metals(Extractive
Metallurgy), 1988, p. 13.
[20] J. Ji, X. Lu, M. Cai, Z. Xu, Improvement of leaching process of Geniposide with
ultrasound, Ultrason. Sonochem. 13 (2006) 455–462.
[21] R. Zhang, X. Zhang, S. Tang, A. Huang, Ultrasound-assisted HCl–NaCl leaching of
lead-rich and antimony-rich oxidizing slag, Ultrason. Sonochem. 27 (2015)
187–191.
[22] X. Wang, C. Srinivasakannan, X. Duan, J. Peng, D. Yang, S. Ju, Leaching kinetics of
zinc residues augmented with ultrasound, Sep. Purif. Technol. 115 (2013) 66–72.
Chemical Engineering and Processing - Process Intensification 161 (2021) 108293
[23] F. Du, J. Li, X. Li, Z. Zhang, Improvement of iron removal from silica sand using
ultrasound-assisted oxalic acid, Ultrason. Sonochem. 18 (2011) 389–393.
[24] D. Liang, J. Wang, Y. Wang, F. Wang, J. Jiang, Behavior of tannins in germanium
recovery by tannin process, Hydrometallurgy 93 (2008) 140–142.
[25] G. Xia, M. Lu, X. Su, X. Zhao, Iron removal from kaolin using thiourea assisted by
ultrasonic wave, Ultrason. Sonochem. 19 (2012) 38–42.
[26] B. Niemczewski, Cavitation intensity of water under practical ultrasonic cleaning
conditions, Ultrason. Sonochem. 21 (2014) 354–359.
[27] S. Dey, V.K. Rathod, Ultrasound assisted extraction of β-carotene from Spirulina
platensis, Ultrason. Sonochem. 20 (2013) 271–276.
[28] J. Raso, M. P, R. Pagán, F.J. Sala, Influence of different factors on the output power
transferred into medium by ultrasound, Ultrason. Sonochem. 5 (1999) 157.
[29] L. Xu, W. Chu, N. Graham, A systematic study of the degradation of dimethyl
phthalate using a high-frequency ultrasonic process, Ultrason. Sonochem. 20
(2012) 892–899.
[30] B. Avvaru, S. Roy, S. Chowdhury, K. Hareendran, A.B. Pandit, Enhancement of the
leaching rate of uranium in the presence of ultrasound, Ind. Eng. Chem. Res. 45
(2006) 7639–7648.
[31] J. Chang, E. Zhang, L. Zhang, J. Peng, J. Zhou, C. Srinivasakannan, C. Yang,
A comparison of ultrasound-augmented and conventional leaching of silver from
sintering dust using acidic thiourea, Ultrason. Sonochem. 34 (2017) 222–231.
[32] M.H. Entezari, P. Kruus, Effect of frequency on sonochemical reactions II.
Temperature and intensity effects, Ultrason. Sonochem. 3 (1996) 19–24.
[33] M. ÖZacar, A. Sengil, H. Türkmenler, Equilibrium and kinetic data, and adsorption
mechanism for adsorption of lead onto valonia tannin resin, Chem. Eng. J. 143
(2008) 32–42.
[34] L. Chupin, C. Motillon, C.E. Bouhtoury, A. Pizzi, B. Charrier, Characterisation of
maritime pine (Pinus pinaster) bark tannins extracted under different conditions by
spectroscopic methods, FTIR and HPLC, Ind. Crops Prod. 49 (2013) 897–903.
[35] J. Zhang, C. Xue, H. Ma, Y. Ding, S. Jia, Fabrication of PAN electrospun nanofibers
modified by tannin for effective removal of trace Cr(III) in organic complex from
wastewater, Polymers 12 (2020).
[36] Z. Xia, A. Singh, W. Kiratitanavit, R. Mosurkal, J. Kumar, R. Nagarajan, Unraveling
the mechanism of thermal and thermo-oxidative degradation of tannic acid,
Thermochim. Acta 605 (2015) 77–85.
[37] W. Zhang, Z. Yang, R. Tang, J. Guan, Y. Qiao, Application of tannic acid and
ferrous ion complex as eco-friendly flame retardant and antibacterial agents for
silk, Journal of Cleaner Production, 250.
[38] G. Socrates, Infrared and Raman Characteristic Group Frequencies: Tables and
Charts, 3rd Edition, Proteomics, 2004.
[39] J.V. Nardeli, C.S. Fugivara, M.G. Taryba, E.R.P. Pinto, A.V. Benedetti, Tannin: A
natural corrosion inhibitor for aluminum alloys, Prog. Org. Coat. 135 (2019)
368–381.
[40] F.ábiodos Santos Grasel, Marco Flres Ferro, Carlos Rodolfo Wolf, Development of
methodology for identification the nature of the polyphenolic extracts by FTIR
associated with multivariate analysis, Spectrochim. Acta A. Mol. Biomol. Spectrosc.
153 (2016) 94–101.
[41] L. Yang, J. Xue, L. He, L. Wu, Y. Ma, H. Chen, H. Li, P. Peng, Z. Zhang, Review on
ultrasound assisted persulfate degradation of organic contaminants in wastewater:
Influences, mechanisms and prospective, Chemical Engineering Journal, 378.
[42] Y. Tao, J. Cai, X. Huai, B. Liu, Z. Guo, Application of hydrodynamic cavitation to
wastewater treatment, Chem. Eng. Technol. 39 (2016) 1363–1376.
[43] N.S.M. Yusof, B. Babgi, Y. Alghamdi, M. Aksu, J. Madhavan, M. Ashokkumar,
Physical and chemical effects of acoustic cavitation in selected ultrasonic cleaning
applications, Ultrason. Sonochem. (2015) 568.
[44] F.J. Fuchs, Ultrasonic Cleaning: Fundamental Theory and Application, 1995.
[45] S.P.E. Anris, A. Bikoro, B. Athomo, R.S. Tchiama, B. Charrier, The condensed
tannins of Okoume (Aucoumea klaineana Pierre): a molecular structure and
thermal stability study, Sci. Rep. Ist. Super. Sanita 10 (2020).
[46] S. Wang, Y. Li, Treatment of residual solution of germanium chloridizing
distillation, Chin. J. Rare Metals (2007).
[47] S. Pu, Y. Lan, L. Jin, C. Xiao, Improving germanium distillation recovery rate from
coal dust, Chinese J. Rare Met. (2012).