Ultrasonics Sonochemistry 106 (2024) 106881

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Application of ultrasonic-enhanced active seed crystals in the removal of

sodium oxalate from alumina refinery waste liquor
Haisheng Duan a, b, Jianfeng Ran a, Jiaping Zhao a, b, Xuxu Wang a, Benkang Zhai a, Ying Chen b,
Shaohua Yin a, *, Shiwei Li a, Libo Zhang a, *, Zulai Li c
a
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650093, China
b
Yunnan Wenshan Aluminum Co., Ltd., Wenshan, Yunnan 663000, China
c
Faculty of Material Science and Engineering, 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: When organic matter, especially sodium oxalate (Na2C2O4), accumulates to a certain extent, it will seriously
Sodium oxalate affect the alumina production process in the refinery and therefore urgently needs to be removed. This work
Ultrasonic attempts to illuminate the benefits of ultrasonic intensification of the crystallization process of Na2C2O4, taking
Flat plate washing liquor
the alumina refinery waste liquor, i.e., flat plate washing liquor, as a case study. The effects of different operating
Organics
parameters (seed crystal addition amount, caustic soda concentration, reaction time, ultrasonic power) on the
Alumina
crystallization behavior and yield are discussed, and it is found that ultrasonic can increase the Na2C2O4 removal
rate to 70.4%. The addition of ultrasonic promotes the morphological evolution of Na2C2O4 and is of great
significance to the optimization of the components of the precipitated Na2C2O4. Specifically, the proportion of
Na2C2O4 in the crystallized product reaches 64% with conventional conditions, while it reaches 77% with ul­
trasonic conditions. Therefore, ultrasonic can greatly reduce the alkali loss caused by the crystallization process
of Na2C2O4 in flat plate washing liquor, which has great economic benefits.

1. Introduction carboxylic cellulose, polysaccharides, lipids, and humic acids existing in

As the third most abundant element in the Earth’s crust, aluminum
(Al) has been widely applied in the building, automotive, electrical
distribution industries, etc. and especially commonly used in the
metallic items [1,2]. Correspondingly, its oxides alumina (Al2O3)
possess wide industrial applications, and the most massive-scale use for
alumina production [3,4]. Currently, Bayer process is considered as the
most significant method for producing alumina in the world, where 95
%-97 % of alumina is carried out by this process [5]. The main feed
bauxite is firstly digested by extremely high concentration caustic so­
lution with pressure and temperature (at 140–155 ◦ C for gibbsite or
220–270 ◦ C for boehmite) to form the hot sodium aluminate solution
[6]. A variety of strong alkaline waste liquors can be produced
throughout the Bayer process, among which flat plate washing liquor
can be produced during the aluminum hydroxide washing stage.
During the digestion process, some organic compounds existing in
the bauxite feed will also react with caustic solution and enter the flat
plate washing liquor. It is reported that the organic matters such as
bauxite (the grade organic carbon of bauxites appears an overall average
of 0.27 %) are considered to be the main source for organics, and
generate some organic acid anions after reacting with sodium hydrox­
ide, e.g., acetates, aromatic compounds, such as high molecular weight
carboxylic acid and humates [7–10]. In addition to humic acids, a small
number of organics from the used flocculant, flotation and anti-foam
agents are also present in the flat plate washing liquor. These humic
acids gradually break down into small molecules throughout the pro­
cessing with the alkaline environment and temperature and pressure
(~0.1 MPa) [11,12], resulting an increasing concentration for sodium
oxalate (Na2C2O4) and carbonate (Na2CO3). According to the study from
Authier-Martin et al. [13], around 2–16 % and 10–51 % of organic
carbon can be degraded into oxalate and sodium carbonate, respec­
tively. Thus, comparing with the minor present organic compounds
mentioned above, Na2C2O4 occupies a significant and exclusive posi­
tion, and is considered as the only degradation product due to its for­
mation rate over the level of solubility in flat plate washing liquor
[14–17]. Therefore, the production of carbonate and oxalate resulting

* Corresponding authors.
E-mail addresses: yinsh@kust.edu.cn (S. Yin), zhanglibopaper@126.com (L. Zhang).

https://doi.org/10.1016/j.ultsonch.2024.106881
Received 5 March 2024; Received in revised form 15 April 2024; Accepted 19 April 2024
Available online 20 April 2024
1350-4177/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
H. Duan et al.
Table 1
Composition and characteristics of flat plate washing liquor.
Composition NT Nk Al2O3 Na2C2O4
Concentration (g/L) 114.20 106 63.48 2.53
Note: αk: 2.75; Temperature: 40 ℃; NC/NT: 7.18%.
from the degradation of humic acids in the Bayer process is undesirable.
As is known, the organic matters existing in flat plate washing liquor
will pose negative effects on the physical and chemical properties of the
sodium aluminate solutions if not treated effectively, e.g., changing
boiling point, viscosity, specific heat, density, and liquor foam [18–21].
After accumulating to a high amount for the organics especially
Na2C2O4, the production process of alumina will be severely affected.
For example, it can lower seed decomposition rate, reduce alumina
production yield, prolong seed induction period, loss sodium hydroxide,
decrease the particle size of aluminum hydroxide, and generate odor
gases, with lowering the alumina whiteness and even diminishing the
red mud settling rate [19,22–27]. Given the considerable hazards caused
by the organics to the Bayer process, much attention has been paid to the
treatment of organic compounds from sodium aluminate solution
including thermal treatment [25], chemical precipitation [10], photo­
catalytic degradation [28], membrane separation [11], and wet oxida­
tion methods [29]. Among them, wet oxidation process is regarded as
the common method available for the removal of organics from sodium
aluminate liquor due to its efficient removal, extensive source of raw
materials and green operation. However, wet oxidation treatment often
has difficulty in completely mineralizing organic matter, and usually
only converts it into Na2C2O4, causing its concentration to increase. It is
reported that the presence of Na2C2O4 can lower the product strength
Fig. 1. Schematic diagram of experimental device.
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Ultrasonics Sonochemistry 106 (2024) 106881
and particle, along with introducing soda impurity, as a result of the
crystalline Na2C2O4 and its interaction with gibbsite solids, which
stimulates the formation of gibbsite nuclei and then prevents them from
agglomerating [30]. Thus, the removal of Na2C2O4 has become a serious
issue due to its complex effects that are difficult to treat using conven­
tional treatment methods. Currently, Hao et al. [31], from Yunnan
Wenshan Aluminum Co., Ltd. propose a new method for removal of
organic matter in alumina mother liquor by aluminum ash sintering
process, and has been successfully implemented, which can realize
disposal and comprehensive utilization of aluminum ash and meantime
reduce the effect of organics on the Bayer system. However, few re­
searches have been conducted on the removal of Na2C2O4 from sodium
aluminate liquor using ultrasound-assisted crystallization techniques
based on the previous studies.
As is known, crystallization plays a crucial role in the separation-
purification step from the solution, but this is often restricted by a low
rate and non-uniform supersaturation in the mixture [32]. As an
intensification method such as ultrasound, has been attracted much
attention due to its cavitation effect. Literature [33] point out that the
limitation of conventional crystallization can be improved by ultrasound
application, and the nucleation, supersaturation, crystal growth in the
crystallization process can be effectively controlled. Currently, there are
few reports dealing with ultrasound application for crystallization
improvement of Na2C2O4. The present work attempts to illuminate the
process intensification benefits from ultrasound-assisted crystallization
techniques for the Na2C2O4, and discusses the effect of different opera­
tion parameters (seed crystal addition, caustic alkali concentration, re­
action duration, ultrasonic power) on the crystal behavior and yield of
Na2C2O4.
H. Duan et al. Ultrasonics Sonochemistry 106 (2024) 106881

Fig. 2. Effect of different seed crystal addition on (a) residual Na2C2O4 concentration, and (b) Na2C2O4 removal rate. (Conventional condition: reaction duration = 5
h, caustic alkali concentration = 210 g/L; Ultrasonic condition: reaction duration = 5 h, caustic alkali concentration = 210 g/L, ultrasonic power = 100 W).

2. Materials and methodology
2.1. Materials
The flat plate washing liquor is provided by Yunnan Wenshan
Aluminum Co., Ltd., China. Specifically, it is a flat plate washing liquid
after aluminum hydroxide washing, and its composition and charac­
teristics are shown in Table 1. Sodium hydroxide (NaOH, AR) is pur­
chased from Tianjin Zhiyuan Chemical Reagent Co., Ltd. (Tianjin,
China), and without further purification. The seed crystal comes from
Yunnan Wenshan Aluminum Co., Ltd., China, and is Na2C2O4 solid
powder obtained from the flat plate washing liquor through conven­
tional crystallization method.
seed crystal addition and caustic alkali concentration, and keep it warm
at 40 ◦ C in a constant temperature water bath. Then, the stirrer is
implemented at a speed of ~ 400 r/min, and the ultrasonic device (2.0
kW, 25 kHz, WM-2000 T, homemade equipment) is turned on syn­
chronously (Fig. 1). Ensure that the volume of the solution before and
after the reaction remains unchanged by adding deionized water. Sub­
sequently, the filtered flat plate washing liquor is further analyzed for
Na2C2O4 content by an ion chromatograph (ECO-IC, Metrohm,
Switzerland).
3. Results and discussion
3.1. Effect of seed crystal addition

Effect of different seed crystal addition (i.e., 10, 20, 50, 80, and 100
2.2. Experimental process and setup
g/L) on Na2C2O4 removal in conventional and ultrasonic is conducted,
as shown in Fig. 2. Adding active seed crystals to the flat plate washing
Select 0.5 L of flat plate washing liquor, the appropriate quality of

Fig. 3. Effect of different reaction duration on (a) residual Na2C2O4 concentration, and (b) Na2C2O4 removal rate. (Conventional condition: seed crystal addition =
20 g, caustic alkali concentration = 210 g/L; Ultrasonic condition: seed crystal addition = 20 g, caustic alkali concentration = 210 g/L, ultrasonic power = 100 W).

3
H. Duan et al.
Fig. 4. Effect of different caustic alkali concentration on (a) residual Na2C2O4 concentration, (b) Na2C2O4 removal rate, (c) phase composition with conventional,
and (d) phase composition with ultrasonic. (Conventional condition: seed crystal addition = 20 g, reaction duration = 5 h; Ultrasonic condition: seed crystal addition
= 20 g, reaction duration = 5 h, ultrasonic power = 100 W).
liquor can induce the precipitation of Na2C2O4 and reduce its equilib­
rium concentration. Therefore, the higher of seed crystal addition in the
range of 10–20 g, the faster precipitation rate of Na2C2O4 in flat plate
washing liquor, and the lower of residual Na2C2O4 concentration.
However, as the seed crystal addition further increases in the range of
20–100 g, the viscosity of flat plate washing liquor increases signifi­
cantly and its settling performance also significantly deteriorates.
Therefore, excessively increasing the seed crystals addition will not
significantly improve the removal effect of Na2C2O4, and filtration will
be more difficult.
When the seed crystal addition is 20 g, the removal rates of Na2C2O4
by conventional method and ultrasonic are 61.3 % and 70.4 % respec­
tively, so ultrasonic significantly improves the crystallization rate.
Additionally, the results of 20 g seed crystals with ultrasonic conditions
are similar to the results of 100 g seed crystals with conventional con­
ditions, indicating that ultrasonic can effectively reduce the seed crystals
addition and improve economic benefits. Cavitation effect is the main
implementation method of ultrasonic, and the evolution process of
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Ultrasonics Sonochemistry 106 (2024) 106881
cavitation bubbles includes nucleation, oscillation, contraction, and
implosion [34–36]. The explosion process can form a local high tem­
perature (5000 K) and high pressure (105 kPa) area, and generate shock
waves or high-speed microjets, which increase the diffusion coefficient
and collision frequency of the solute molecules, and ultimately accel­
erate the crystallization process [37,38]. Specifically, ultrasonic can
improve the precipitation efficiency of Na2C2O4 compared with con­
ventional methods by increasing the collision frequency between C2O2- 4
and seed crystals. Hence, the seed crystal addition is selected to be 20 g.
3.2. Effect of reaction duration
Effect of different reaction duration (i.e., 1, 3, 5, 8, and 12 h) on
Na2C2O4 removal in conventional and ultrasonic is compared, as shown
in Fig. 3. Prolonged the reaction duration can facilitate the Na2C2O4
crystallization process with conventional condition. Therefore, the
longer reaction duration, the greater precipitated amount of Na2C2O4 in
flat plate washing liquor. Ultrasonic can promote the nucleation of
H. Duan et al.
Fig. 5. Effect of different ultrasonic power on (a) residual Na2C2O4 concentration, and (b) Na2C2O4 removal rate. (Ultrasonic condition: seed crystal addition = 20 g,
reaction duration = 5 h, caustic alkali concentration = 210 g/L).
Na2C2O4 compared with conventional method, increase its precipitation
rate, and further reduce its equilibrium concentration. When the reac­
tion duration is 5 h, the removal rates of Na2C2O4 by conventional and
ultrasonic method are 61.3 % and 70.4 % respectively, so ultrasonic
significantly improves the crystallization rate. Furthermore, the results
of 5 h reaction duration with ultrasonic conditions are similar to the
results of 12 h reaction duration with conventional conditions. The
positive effect of ultrasonic in shortening the reaction duration comes
from the continuous symmetric collapse and implosion during the
cavitation process, which produces strong microjets and then changes
the metastable state generated by hydrogen bonds [34,38,39]. In
particular, the microjets near the solid–liquid interface reduce the
boundary layer thickness through turbulence effect and increase the
mass transfer rate [40,41]. In addition, ultrasonic can increase the
conductivity of the supersaturated solution, reduce the viscosity of the
solution, and shorten the induction period of crystal nucleation, which is
conducive to the precipitation of crystals from the supersaturated so­
lution [42,43]. Hence, the reaction duration is selected to be 5 h.
3.3. Effect of caustic alkali concentration
Effect of different caustic alkali concentrations (i.e., 180, 210, 240,
270, and 300 g/L) on Na2C2O4 removal in conventional and ultrasonic is
conducted, as shown in Fig. 4(a) and (b). The solubility product constant
of Na2C2O4, is constant at the same temperature. When the caustic alkali
concentration (i.e., Na+ content) of flat plate washing liquor is
increased, the Na2C2O4 ion concentration with equilibrium conditions
decreases. This may be because at the same temperature, the solubility
product Ksp of Na2C2O4 (Ksp = [Na]2•[C2O2- 4 ]) remains unchanged. The
higher the content of free sodium ions, the lower the solubility of
Na2C2O4. Therefore, the higher caustic alkali concentration, the greater
precipitated amount of Na2C2O4 in flat plate washing liquor. Ultrasonic
can promote the nucleation of Na2C2O4 compared with conventional
method, increase its precipitation rate, and further reduce its equilib­
rium concentration. When the caustic alkali concentration is 210 g/L,
the removal rates of Na2C2O4 by conventional and ultrasonic method are
61.3 % and 70.4 % respectively, so ultrasonic significantly improves the
crystallization rate. However, as the caustic alkali concentration is
further increased, the viscosity of flat plate washing liquor gradually
increases, causing the strengthening effect of ultrasonic to be gradually
weakened. Furthermore, the results of 210 g/L caustic alkali
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Ultrasonics Sonochemistry 106 (2024) 106881
concentration with ultrasonic conditions are similar to the results of 240
g/L caustic alkali concentration with conventional conditions, indi­
cating that ultrasonic can effectively reduce the seed crystals addition
and improve economic benefits. Hence, the caustic alkali concentration
is selected to be 210 g/L.
The composition of the Na2C2O4 precipitate obtained with conven­
tional conditions and ultrasonic conditions is analyzed, as shown in
Fig. 4(c) and (d). When the caustic alkali concentration is 210 g/L with
conventional conditions, the proportion of Na2C2O4 reaches the
maximum value of 64 %. Subsequently, the proportion of Na2CO3
increased as the caustic alkali concentration is further increased, and
reached 53 % at 300 g/L. However, the proportion of Na2C2O4 in the
crystallized filter cake first increases and then decreases with ultrasonic
conditions, and reaches a maximum value of 77 % when the caustic
alkali concentration is 210 g/L. Subsequently, when the caustic alkali
concentration is 300 g/L, Na2C2O4 is still the main component of the
filter cake. Further comparison shows that at the same caustic alkali
concentration, the proportion of Na2C2O4 with ultrasonic conditions is
significantly higher than that with conventional conditions. This may be
because the physical and chemical properties of the flat plate washing
liquor are changed by ultrasonic, thereby reducing the solubility of
Na2C2O4 in it and accelerating crystallization [42,44,45].
3.4. Effect of ultrasonic power
Effect of different ultrasonic powers (i.e., 0, 20, 50, 100, 150, and
200 W) on Na2C2O4 removal in conventional and ultrasonic is con­
ducted, as shown in Fig. 5. Regarding the mechanism of ultrasonic-
enhanced solution crystallization, the generally accepted view is that a
series of changes from cavitation bubbles are the main factors that
promote the crystallization reaction [46,47]. The cavitation bubbles go
through an expansion period, a compression period and an implosion
period in the solution, causing changes in the energy of the local system
and generating new free radicals and broken ions. Specifically, it breaks
the metastable state of the solution, increases the degree of supersatu­
ration, and promotes the precipitation of crystals.
It can be found that as the ultrasonic power gradually increases, the
residual Na2C2O4 concentration in flat plate washing liquor first de­
creases and then increases. When the ultrasonic power is 100 W, the
removal rate of Na2C2O4 by ultrasonic is 70.4 %, so ultrasonic signifi­
cantly improves the crystallization rate. According to crystallization
H. Duan et al. Ultrasonics Sonochemistry 106 (2024) 106881

Fig. 6. SEM and EDS elemental mapping images at different ultrasonic power: (a) 0 W, (b) 20 W, (c) 50 W, (d) 100 W, (e) 150 W, and (f) 200 W.

6
H. Duan et al.
Fig. 7. Results for Na2C2O4 at different ultrasonic power. (a) XRD patterns, (b) diffraction peak intensity, (c) FWHM and grain size, (d) relative crystallinity.
theory, ultrasonic has both positive and negative effects on crystal
growth [48,49]. On the one hand, ultrasonic cavitation reduces the
thickness of the interfacial solute layer, thereby accelerating the diffu­
sion process of solute molecules. On the other hand, the generated micro
jets have a denting effect on the crystal surface, and excessive power
may even break the crystal. The breakage of crystals in solution can also
cause secondary nucleation [50,51]. Similarly, Ruecroft et al. [52] have
reported that excessive ultrasonic power can easily induce secondary
nucleation, causing secondary growth of crystals. Hence, the ultrasonic
power is selected to be 100 W.
In summary, the optimal experimental conditions are identified: seed
crystal addition; 20 g, caustic alkali concentration; 210 g/L, reaction
duration; 5 h, ultrasonic power; 100 W.
The crystallization habit of a crystal is mainly determined by the
chemical composition and crystal structure of the crystal, and is also
closely related to external conditions (e.g., temperature, pressure, con­
centration, viscosity, impurities). The SEM and EDS elemental mapping
images of Na2C2O4 in flat plate washing liquor with different ultrasonic
powers are comparatively analyzed, as shown in Fig. 6. The Na2C2O4
precipitated without ultrasonic is an elongated crystal, indicating that
its axial growth rate is greater than the radial growth rate, which may be
related to the presence of organic matter such as sodium humate in flat
7
Ultrasonics Sonochemistry 106 (2024) 106881
plate washing liquor. Such organic matter will reduce the surface ac­
tivity of Na2C2O4 crystals and inhibit their growth.
As the ultrasonic power increases from 20 W to 100 W, the sharp
needle-like Na2C2O4 morphology becomes less and less, and the pro­
portion of flake or block morphology gradually increases. The existence
of needle-shaped Na2C2O4 can no longer be clearly observed when the
ultrasonic power reaches 100 W. And when the ultrasonic power is
further increased, the morphology does not change much. Further EDS
elemental mapping images show that the precipitated Na2C2O4 crystals
contain a variety of elements, e.g., Na, O, C, Al, K, and Cl. The C content
in the precipitate shows a trend of first increasing and then decreasing
with the increase of ultrasonic power, and reaches a maximum value of
22.1 % at 100 W, indicating that the Na2C2O4 content is highest.
Na2C2O4 crystals will agglomerate in the absence of ultrasonic,
appearing radially or umbrella-shaped, and the agglomeration starting
point is at both ends of the longer side of the crystal, resulting in the
crystal being columnar, needle-shaped, fibrous, etc. On the contrary,
ultrasonic has multiple effects on supersaturated solutions, such as
greatly increasing the nucleation rate of the solution, directionally
changing the crystal morphology, and improving crystal dispersion.
The fine needle-shaped Na2C2O4 crystals precipitated with conven­
tional conditions can promote the production of large amounts of
H. Duan et al. Ultrasonics Sonochemistry 106 (2024) 106881

Fig. 8. SEM images of products at different reaction duration: (a) 1 h, (b) 3 h, (c) 5 h, (d) 8 h, (e) 12 h. (Condition: seed crystal addition = 20 g, caustic alkali
concentration = 210 g/L, ultrasonic power = 100 W).

Fig. 9. Schematic diagram of the mechanism of ultrasonic-assisted crystal growth.

8
H. Duan et al.
aluminum hydroxide fine particles for the following reasons: (i) it can
serve as secondary crystal nuclei to promote the nucleation of aluminum
hydroxide, and (ii) it can also crystallize and precipitate on the surface of
aluminum hydroxide or in the gaps between particles, seriously hin­
dering the agglomeration of aluminum hydroxide. However, the
precipitated Na2C2O4 crystals are mainly in the form of flakes or blocks
after the action of ultrasonic, which can significantly improve the above-
mentioned harmful behaviors.
The XRD pattern of Na2C2O4 in flat plate washing liquor at different
ultrasonic powers are comparatively analyzed, as shown in Fig. 7(a). It
can also be seen that the precipitated Na2C2O4 is a mixture composed of
Na2C2O4 (JCPDS card no. 49–1816), Na2CO3 (JCPDS card no. 08–0448),
and NaOH (JCPDS card no. 85–0732). However, the XRD peaks of the
products with different ultrasonic powers are different (Fig. 7(b)). As the
ultrasonic power increases, the diffraction peak intensity of the precip­
itated Na2C2O4 crystals shows a trend of first increasing and then
decreasing, and reaches the strongest at 100 W, indicating that its
crystals produced have optimal crystallinity. This may be due to the
different orientations of its crystals, which lead to different x-ray scat­
tering intensities, thereby affecting the diffraction peak intensity.
The results of FWHM and grain size (Fig. 7(c)) indicate that ultra­
sonic power has a greater impact on the integrity of the crystallized
product. Specifically, the FWHM of Na2C2O4 shows a trend of first
decreasing and then increasing as the ultrasonic power increases, while
the change in grain size is just the opposite. The relative crystallinity
results (Fig. 7(d)) show that the relative crystallinity of the product
shows a trend of first increasing and then decreasing with the increase of
ultrasonic power, and reaches the highest point of 57.46 % at 100 W,
indicating that the crystal quality of the product is the best.
3.5. Ultrasonic induced crystallization mechanism
To further study the mechanism of ultrasonic-induced crystalliza­
tion, SEM characterization of the products with different reaction
duration with the ultrasonic power of 100 W is performed (Fig. 8). The
cavitation effect of ultrasonic is the main factor in assisting crystalliza­
tion, viz. the expansion period, compression period and implosion
period of cavitation bubble development, as shown in Fig. 9. (i)
Expansion period: since the unsaturation of the crystals in the solution
decreases as the temperature decreases, the change in local temperature
provides a driving force for the crystallization of the solution and pro­
motes further precipitation. (ii) Compression period: the subsequent
sound pressure will shrink in reverse as the cavitation bubbles continue
to expand, causing the local supersaturation of the solution to greatly
increase, and the metastable state of the solution to be broken, which is
conducive to the crystallization reaction. (iii) Implosion period: local
temperature in the solution is greatly increased instantly due to the
absorption of ultrasonic energy by the cavitation bubbles, causing the
inside of the solution to be violently disturbed, and the extremely fast
impact jet causes huge changes in the structure of the solution in a short
period of time, promoting the crystallization reaction. In addition, the
presence of ultrasonic can break the crystallized nuclei in the solution.
Therefore, unlike the needle-like structure that “extends in one direc­
tion” without ultrasonic, the crystallization habit of Na2C2O4 is in the
form of flakes or blocks with the action of ultrasonic, and aggregates into
a spherical shape as the action time increases. However, the nucleation-
promoting properties of ultrasonic are not observed, possibly because of
the large number of seed crystals added at the initial stage of the reac­
tion. In short, continued ultrasonic irradiation will greatly accelerate the
speed of nucleation and crystal growth, and make the precipitated
Na2C2O4 crystals exhibit multi-angle spatial growth properties, which is
consistent with the results of SEM images.
4. Conclusions
The crystallization process of Na2C2O4 from flat plate washing liquor
9
Ultrasonics Sonochemistry 106 (2024) 106881
under conventional conditions and ultrasonic conditions is compara­
tively analyzed, and the influence of different factors on crystallization
behavior is also studied. Through continuous ultrasonic irradiation, the
Na2C2O4 concentration in flat plate washing liquor have dropped from
2.53 g/L to 0.75 g/L, and the removal rate reaches 70.4 % under the
optimal conditions (seed crystal addition; 20 g, caustic alkali concen­
tration; 210 g/L, reaction duration; 5 h, ultrasonic power; 100 W), while
it is only 61.3 % without ultrasonic. Ultrasonic power of 100 W can
maximize the Na2C2O4 content in the crystallized product and signifi­
cantly increase the relative crystallinity of the product, as shown by XRD
analysis. Obtaining 100 W of ultrasonic power can promote the
morphology of Na2C2O4 crystals to develop from sharp needles to flakes
or blocks, as can be seen from SEM analysis. This research lays the
foundation for the ultrasonic-induced crystallization of Na2C2O4 in
Bayer liquid. It has practical significance for improving the performance
of alumina products and will effectively promote the growth of the
global alumina industry.
CRediT authorship contribution statement
Haisheng Duan: Writing – original draft, Software, Methodology,
Investigation, Formal analysis, Conceptualization. Jianfeng Ran: Data
curation. Jiaping Zhao: Visualization. Xuxu Wang: Validation. Ben­
kang Zhai: Software. Ying Chen: Resources. Shaohua Yin: Writing –
review & editing, Supervision, Funding acquisition, Formal analysis,
Conceptualization. Shiwei Li: Writing – review & editing, Supervision.
Libo Zhang: Writing – review & editing, Funding acquisition. Zulai Li:
Investigation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work is supported by Yunnan Major Scientific and Technolog­
ical Projects (Grant No. 202402AB080004 and 202202AG050011).
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