Waste Management 177 (2024) 169–176

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Research Paper

Red mud-based perovskite oxygen carrier preparation for chemical looping

gasification of municipal sludge
Kun Wang a, Xiaoying Yuan a, Wenzheng Liang a, Sheng Yao a, Jialu Li a, Cuiping Wang a, *,
Guangxi Yue b
a
Clean Energy Lab, Shandong University of Science and Technology, Qingdao 266590, China
b
Department of Energy and Power Engineering, Tsinghua University, Beijing,100084

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

Keywords: Chemical looping gasification (CLG) is a promising technology that utilizes lattice oxygen for partial oxidation of
Red mud solid organic waste to produce high-quality syngas. The utilization of low-cost and high-performance oxygen
Perovskite oxygen carrier carriers (OCs) is important for the success of this technology. The red mud from aluminum production was mixed
Municipal sludge
with calcium and manganese oxides to prepare CaMn0.5Fe0.5O3-δ perovskite OCs. The comparative redox tests
Chemical looping gasification
Hydrogen-rich gas
were carried out to analyze the reactivity using a thermogravimetric analyzer (TGA). Multiple cycle CLG ex­
periments were conducted on a wet municipal sludge in a lab-scale fluidized bed to produce the hydrogen-rich
gas. The results showed that the CaMn0.5Fe0.5O3-δ-washed demonstrated higher oxygen transfer capacity and
better cycling stability with a maximum weight loss of 7.3096 %. After the 5th cycle in CLG, the syngas obtained
using CaMn0.5Fe0.5O3-δ-washed maintained a H2 volume fraction exceeding 40%. However, an increase in CO2
production was also observed, which could be due to the catalytic effect of MnO in the OC on the steam-
reforming reaction. The XRD curves showed that fresh CaMn0.5Fe0.5O3-δ-washed exhibited prominent diffrac­
tion peaks characteristic of perovskite. It was observed that after undergoing 5 cycles, the presence of iron
calcium silicate structures containing Mn became evident due to the attachment of sludge ash, leading to the
increased impurities on the surface of OCs with a decrease in the specific surface area. Additionally, some of the
reacted OC particles exhibited a hollow structure, facilitating the fluidization. This preliminary study provides
the basis for the improvement of the OC performance in sludge gasification.

1. Introduction achieving a disposal rate of over 90 % by 2025 (Zhi et al., 2024).

As of now, many researchers have achieved excellent results in the
As a response to the global climate change challenge, China proposed preparation of hydrogen-rich gas from the sludge (Yan et al., 2020).
an important dual-carbon strategy in 2020 intending to peak carbon Domínguez et al. (Domínguez et al., 2006) employed high-temperature
emissions by 2030 and achieve carbon neutrality by 2060 (Sun et al., pyrolysis of wet sewage sludge to produce synthesis gas with a hydrogen
2022; Hu et al., 2022). To achieve these goals, it is crucial to pay special concentration greater than 35 vol%. Upon comparing the two hydrogen
attention to the resource utilization of solid waste (Zhu et al., 2023). production methods, pyrolysis, and steam gasification, Nipattummakul
Sludge is one of the solid by-products generated during wastewater et al. (Nipattummakul et al., 2010) found that steam gasification
treatment, and its production is significantly growing annually (Zat resulted in higher H2 content compared to pyrolysis. Additionally,
et al., 2021; Penido et al., 2019). The existing sludge disposal technol­ sludge gasification in fluidized beds showed higher efficiency compared
ogies primarily involve drying and incineration, with landfilling and to fixed-bed reactors (Nipattummakul et al., 2010). However, in these
composting as secondary methods (Huang et al., 2018). However, these studies, the production of hydrogen gas typically involved using dried
methods are not environmentally friendly as they lead to great energy sludge, with external water vapor then introduced. This greatly in­
consumption wasting the resource potential of the sludge as organic creases energy consumption and costs. In this research, the sludge of
solid fuel (Zhang et al., 2017). The current resource utilization rate in moisture about 50–55 % was directly utilized for chemical looping
China is around 60 %, falling significantly short of the target of gasification to save energy.

* Corresponding author at: Clean Energy Lab, Shandong University of Science and Technology, Qingdao 266590, China.
E-mail address: wangcuiping21@sdust.edu.cn (C. Wang).

https://doi.org/10.1016/j.wasman.2024.01.042
Received 10 October 2023; Received in revised form 17 December 2023; Accepted 26 January 2024
Available online 7 February 2024
0956-053X/© 2024 Elsevier Ltd. All rights reserved.
 K. Wang et al. Waste Management 177 (2024) 169–176

Chemical looping (CL) technology utilizes the continuous reduction 2. Materials and methods
and oxidation of the oxygen carrier within two interconnected reactors
(fuel reactor (FR) and air reactor (AR)) to achieve oxygen transfer and 2.1. Preparation of CaMn0.5Fe0.5O3-δ type OC
thermal conversion of fuel (Zeng et al., 2016; Zhao et al., 2021). CLG of
sludge, aimed at reducing pollution and carbon emission, is different Red mud sample from Shandong Lubei Enterprise Group Corporation
from the traditional co-combustion in power plants that require special was subjected to grinding, drying, and screening, to obtain a particle size
sludge drying (Shen et al., 2021; Liu et al., 2018). By adjusting the OC of less than 75 μm, using a 200-mesh sieve. The chemical composition
ratio, wet sludge particles could be converted into hydrogen-rich gas and content of the sample were determined using X-Ray fluorescence
through pyrolysis (Wang et al., 2021; Sun et al., 2023). As an excellent (XRF, Japan RIGAKU ZSX Priums) as shown in Table S1.
carrier, economic and batch preparation are the key factors (Kuo et al., The preparation process of OC is shown in Fig. 1. Red mud powder
2018; Zhang et al., 2022). Iron oxide has a wide range of applications in was weighed and then washed with deionized water to remove most of
the CL treatment of sludge due to its easy availability and relatively high the sodium ions. The pH of the leachate after deionized water washing
reactivity. This approach is environmentally friendly, as it involves was keeping tested, when it reached 7.5–8, red mud was considered to
utilization of industrial solid waste or natural ore as raw materials for be ready for use. It was then placed in an air-drying oven and dried at
the preparation of oxygen carriers (OC) (Wang and Zhao, 2016). 105 ◦ C for 4 hr till constant weight. A specific quantity of analytically
Red mud is a solid waste generated in the Bayer aluminum industry. pure CaO and MnO2 powders were mixed to ensure that the moles of Ca,
The main components of red mud are Fe2O3, SiO2, Al2O3, CaO, and it Fe, and Mn in the powders matched the stoichiometric ratio required for
also contains high levels of alkalis and fluorides as pollutants. It is CaMn0.5Fe0.5O3-δ. To ensure adequate strength, ultra-fine cement was
difficult to handle owing to its high alkalinity, fine particle size, and used as the molding binder for the OC, in a mass ratio of 2:1. The powder
large quantity (Song and Xu, 2023). Current disposal methods for the red material was thoroughly mixed and granulated in a disc granulator. A
mud mainly involving burning to produce building materials and con­ 40 % solution of water glass was sprayed as a forming agent during the
structing dam storage, also pollute the ecological environment, hin­ granulation process and OC particles with a size of 1–2 mm were
dering the achievement of the 11th (Sustainable cities and communities) screened for utilization. The OC particles were subsequently placed in an
sustainable development goals (SDGs). Nevertheless, red mud contains air blast drying oven at 105 ◦ C for 6 hr to cure. These particles were
abundant substances such as Fe2O3, Al2O3, and CaCO3, making it an subjected to heat treatment in a muffle furnace, gradually increasing the
ideal raw material for preparing Fe-based OC and achieving the goal of temperature at 5 ◦ C/min to 850 ◦ C and kept for 3 hr at the final tem­
“treating waste with waste” (Feng et al., 2022). Here, red mud along perature. The furnace was naturally cooled to room temperature to
with CaO and MgO was used as the raw material to prepare CaMn0.5 obtain the prepared perovskite OC, denoted as CaMn0.5Fe0.5O3-
Fe0.5O3-δ type perovskite OC based on our earlier work (Liang et al., δ-washed, CaMn0.5Fe0.5O3-δ-washed-cement, and CaMn0.5Fe0.5O3-δ-not
2023). The high sodium content in the red mud always reduced the washed.
strength of perovskite OC for its lower gasification point and easily
evolution when the OC was calcinated and sludge chemical looping 2.2. Preparation of high moisture sludge particle
gasification. For the sodium is easy dissolved in water, the sodium
content could be reduced by water washing. Otherwise, cement binder The sludge used in this work was obtained from a municipal sewage
addition is another way to improve the OC strength. The present work treatment plant in the local city of Qingdao. The fuel analysis of this
involves the study of the oxidation–reduction performance of the pre­ sludge was conducted and the results are displayed in Table 1. Because
pared OC for the gasification of municipal wet sludge. Gasification of the of the high viscosity of the high humidity sludge, the granulation process
wet municipal sludge particles eliminated the need for deeply drying becomes difficult. Therefore, a specific quantity of high moisture sludge
and the released vapor acted as the gasification agent to react with (HMS) was placed in an air-drying oven for low-temperature drying at
carbon and CH4, which greatly reduced the energy consumption in 80 ◦ C for 24 hr. The dried sludge was then crushed and screened to
sludge treatment. Sludge gasification process was evaluated by obtain a dry sludge powder with a particle size < 178 μm. After
analyzing the generation of hydrogen-rich synthesis gas and the char­ squeezing the HMS into particles, dried sludge powder was sprayed, and
acterization of the perovskite OC before and after multiple cycles to the HMS particles were covered with powder to prevent their adhesion.
determine the effectiveness of red mud-based OC on sludge gasification. The average moisture content of the sludge particles covered with dry­
ing sludge powder was reduced to 55–60 % before being used as gasi­
fication fuel.

Fig. 1. Schematic diagram of the CaMn0.5Fe0.5O3-δ type OCs preparation process.

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Table 1
Sludge fuel analysis.
Sample Proximate analysis (wt. %) Ultimate analysis (wt. %)
Mar Var FCar Aar Cd Hd Nd Sd Od

HMS 79.82 10.03 1.33 8.82 22.82 3.52 3.43 2.30 24.22

Note: The content of O was calculated by the difference method.

2.3. Experimental corresponding to the critical velocity required for maintaining the flu­
idized state inside the reactor was calculated based on the known data
2.3.1. Thermogravimetric analysis on particle size, the density of the prepared OC, and the internal
15 mg of perovskite OC was used for Thermogravimetric analysis diameter of the reactor. After determining the OC dosage, the optimal
(TGA, German NETZSCH STA449F5). Four temperature control pro­ sludge dosage was determined through subsequent experiments. The
grams were set for the analysis. At first, the perovskite OC was heated to main parameters are included in Table S2.
800 ◦ C from room temperature at a heating rate of 25 ◦ C/min under a The meaning of C/O is defined as Eqs. (1).
nitrogen environment having the flow rate of 20 ml/min. Subsequently, mHWS
the atmosphere was switched to a reducing environment with 50 ml/ C/O = (1)
moc
min of 5 % H2, maintaining a temperature of 800 ◦ C for 40 min to
facilitate the fully release of oxygen. Subsequently, the atmosphere was where mHWS refers to the amount of the HMS fed during the experiment;
switched back to a nitrogen atmosphere with a flow rate of 20 ml/min mOC means the mass of the OC used in the gasification procedure.
and heating was continued at a rate of 25 ◦ C/min till the temperature Gas samples were collected every 3 min from the discharge pipe. A
reached 900 ◦ C. The atmosphere was switched to air with a flow rate of total of three samples were used for subsequent analysis of the syngas
50 ml/min at 900 ◦ C for 30 min to complete one full redox cycle and composition.
then transitioning to the next cycle. Before the experiments, the TG Following the completion of OC regeneration, the reactor was cooled
baselines were premeasured at the same heating rate and carrier gas using low-temperature air until the OC underwent five cycles of oxida­
flow rate without sample loading to reduce buoyancy effects. To ensure tion–reduction. Samples of the OC before and after the reaction were
the reliability and reduce errors of the experimental results, the ther­ taken for characterization to analyze the changes that occurred after the
mogravimetric analysis experiments for samples were repeated one time performance.
under identical conditions.

2.3.2. Multi-cycle CLG in a lab-scale fluidized bed reactor 2.4. Data analysis
The experimental setup for the multi-cycle reaction is shown in
Fig. 2, which mainly includes a fluidized bed reactor, a feeder device, a 2.4.1. Reaction kinetic calculations
preheater, a temperature control device, a dryer, and a flue gas analyzer The reaction activation energy (Ere) and the pre-exponential factor
(KANE9506, UK). The height of the fluidized bed reactor is 1500 mm, (Are) of the perovskite OC were determined using the Arrhenius equation
and the inner diameter at the distributor plate location is 50 mm. Besides based on the thermogravimetric data.
the flue gas analyzer, samples were collected from the gas outlet of the The conversion rate of the OC at t time is defined using the following
fluidized bed reactor after condensation and filtration and were sub­ equation:
jected to gas chromatography for detailed analysis (Thermo Scientific, m0 − mt
ISQ 7000/TRACE 1310). βOC = × 100% (2)
m0 − m∞
Based on previous research, the optimal FR temperature was 800℃,
while the AR was 900 ◦ C (Sun et al., 2023). The gas flow rate where m0 is the initial mass of OC; m∞ is the mass of OC after reaction; mt

Fig. 2. Schematic diagram of lab-scale fluidized bed reactor.

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is the mass of OC at time t in the reaction process. Similarly, the heat value of the syngas reflects the performance of the
The reduction process of the OC occurs in the isothermal phase of the perovskite OC during multiple cycles.
second stage in TGA, following the Avrami-Erofeev equation: The equation for the total outlet gas flow is shown below:

(100 − β)/100 = e− ktn

(3) Fout =
FN2 ,in
∑ (6)
1− yi
ln[ − ln((100 − β)/100)] = nlnt + lnk (4)
The carbon conversion rate can be defined with the following
where βOC is the conversion rate in percent; n is the reaction order. For equation.
the reactions of organic matter, the reaction order usually is less than 2 ∫ t( )
yCO + yCO2 + yCH4 + Fout dt/22.4
(Xu et al., 2021). The four values of 0.5, 1.0, 1.5, and 2.0 were compared ηC = 0 × 100% (7)
mC /12
to obtain the best fit. t is the reaction time in seconds; k is the reaction
rate constant in s− 1 (when the reaction order is 1). Plotting the pairs in where FN2, in is the inlet flow rate of N2; yi is the volume concentration of
Eqs. (4) yields a straight line whose intercept is the logarithmic value of each gas component; i is CO2, CO, CH4, H2; mC is the quality of carbon in
the reaction rate constant and whose slope is the reaction order n. the sludge.
According to Arrhenius’ equation:
lnk = lnAre − (Ere /R)(1/T) (5) 3. Results and discussion

where Are refers to the pre-factor of the reduction process; Ere is the 3.1. Redox characteristics
reflected activation energy of the reduction process in kJ/mol; R is the
ideal gas constant, 8.31 J/(mol/K); T is the thermodynamic temperature Redox reactions were individually conducted for the three types of
of the reaction in Kelvin. The Ere is closely related to T, and it changes CaMn0.5Fe0.5O3-δ during TGA, and the outcomes are illustrated in Fig. 3.
with T. However, within a certain temperature range, the Ere can be According to Fig. 3(a), (b), (c), the overall weight loss process of the
considered approximately constant because the effect of T variation is OC can be divided into three stages. The reduction in stage I mainly
relatively small within this range. Since the value of the reaction acti­ involves oxygen decoupling. A decrease in the amount of oxygen
vation energy remains unchanged over a certain temperature range, the released from manganese oxide was observed in the order from OC
E and k0 are calculated by the intercept and slope of the straight line without sodium washing to the OC with sodium washing and cement
obtained from the linear relationship between ln k and 1/T. binder. It can be attributed to the reduction in the activation sites on
manganese oxide by the action of strong alkali. The process of OC
2.4.2. Performance evaluation of OC on hydrogen-rich gas preparation reduction is reflected in stage II, wherein the weight loss represents the
The volume fraction of the active components (H2 + CO + CH4) in lost proportion of lattice oxygen which is caused of oxygen transfer
the syngas is used as an index to evaluate the quality of the syngas. capacity and reactivity of the carrier. It could be observed that the

Fig. 3. TGA of (a) CaMn0.5Fe0.5O3-δ-not washed; (b) CaMn0.5Fe0.5O3-δ-washed; (c) CaMn0.5Fe0.5O3-δ-washed-cement.

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oxidation process of iron-based OC was faster compared to the reduction 3.3. Effect of cement addition
process. The perovskite OC with a cement shaping material undergoes a
final weight loss of 4.3998 % when calcined at 800 ◦ C. After subtracting To study the effect of cement addition on the performance of the OC,
and normalizing the cement content, it was noticed that the addition of the reaction kinetic parameters of the CaMn0.5Fe0.5O3-δ-washed and the
cement to the OC using sodium-washed red mud had no significant CaMn0.5Fe0.5O3-δ-washed-cement were compared, and the results are
impact on its oxygen transfer capacity. The maximum rate of weight loss shown in the Table S4. The cement binder not only increased the acti­
during the reduction process was − 2.0556 %/min, while the rate of vation energy required for the reaction but also weakened the contact
maximum weight gain during the oxidation process was 7.0277 %/min, between the gas–solid interfaces.
indicating that the carrier could quickly regain weight to nearly its The utilization of cement binder is suitable when the redox reactions
initial state in a short time. The non-washed OC exhibited slower rates of are controlled at low velocity. During gasification, the oxygen demand is
release and uptake reactions of oxygen, indicating that the excessive not substantial, but it may need a faster reaction velocity. Hence, the
alkaline components were not beneficial to the redox activity of the utilization of cement binder for increasing the OC strength may be
perovskite OC. The consistency of the weight gain-loss process of the OC limited in these cases.
indicated good stability of the cyclic reaction activity.
3.4. Analysis of unrecovered oxygen decoupling
3.2. Effect of removal of sodium from red mud by washing
During the oxidation stage, the oxygen released by the perovskite
According to the results of TGA, the CaMn0.5Fe0.5O3-δ-washed sam­
OCs during their reduction stage was not fully recovered, indicating a
ple exhibited superior performance. To explore the reasons behind this,
decoupling of oxygen. Since the oxygen decoupling mainly stems from
the OC was subjected to microstructure analysis by SEM-EDS. These
manganese oxide, the reason for the unrecovered oxygen might be
tests were performed before and after multiple cycles of gasification to
related to the properties of the MnO2 used. To verify this hypothesis, we
observe the distribution of four main elements on the surface of the two
prepared perovskite OC with the same formulation using MnO2 by sol­
OCs. The results of this analysis are shown in Table S3 and the corre­
–gel method with manganese nitrate solution as the precursor. It is clear
sponding diagrams are shown in Fig. 4.
from the TGA results shown in Fig. S1 (a) that the MnO2 prepared by the
The distribution of various elements in the fresh OC particles was
sol–gel method exhibited good decoupling performance, with distinct
relatively uniform, as shown in Fig. 4 (a) and (c). Analysis of the
decoupling stages corresponding to Eqs. (8) and Eqs. (9) respectively.
elemental compositions (Table S3), revealed that washing effectively
removed a portion of Na. However, in the case of the reacted OC (Fig. 4 3MnO2 = Mn3 O4 + O2 (8)
(b) and (d)), Na content increased and the image appeared darker,
possibly due to the attachment of ash from the sludge during the reac­ 2Mn3 O4 = 6MnO + O2 (9)
tion process. The limited solubility of Ca oxide in water caused a slight Based on the results of a single oxygen decoupling regeneration cycle
decrease in the Ca content, after washing, as shown in Fig. 4 (a), while (Fig.S1 (b)), we observed the oxygen decoupling in the initial weight
the carbonation improved the mass ratio of Ca salt, as shown in Fig. 4 loss stage of MnO2 synthesized by the sol–gel method. This process
(b). The comparison of Fig. 4 (c) with Fig. 4 (a) indicated that the active primarily consists of the conversion of MnO to Mn3O4, as the conversion
constituents of Mn and Fe exhibited a slight increase after washing. of MnO2 to MnO typically takes place at higher temperatures. Therefore,
However, the reaction had little influence on their content, resulting in a the observed oxygen decoupling is mainly the reverse process of Eqs. (9).
uniform distribution and brightness as seen in Fig. 4 (d) and Fig. 4 (b). Because the sol–gel synthesis of MnO2 achieved better chemical homo­
geneity and nanoparticulate nature of MnO2, it becomes possible to re-

Fig. 4. Distribution of four major elements on the surface of (a)fresh CaMn0.5Fe0.5O3-δ-washed;(b) reacted CaMn0.5Fe0.5O3-δ-washed; (c) fresh CaMn0.5Fe0.5O3-δ-not
washed and (d) reacted CaMn0.5Fe0.5O3-δ-not washed.

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obtain molecular oxygen. Thus, it is beneficial to incorporate the 3.6. Characterization of perovskite OC
nanoscale MnO2 powder in the new OC preparation.
Using the Japanese Rigaku Ultima IV X-ray diffractometer, the
3.5. Multiple-cycle gasification experiment changes in the crystal structure of the perovskite OC component were
analyzed during gasification, as shown in Fig. 6 (a).
Using different perovskite OCs, CLG of HWS was carried out to As seen in Fig. 6 (a), the repeated cycling processes impacted the
produce synthesis gas. During the gasification process, sampling was crystalline phases of the perovskite component. The fresh OC exhibited a
carried out every 3 min, wherein gas bags were collected in each cycle at good diffraction peak intensity of CaMn0.5Fe0.5O3-δ. However, after
3 and 6 min. The gas chromatographic data was analyzed and the results cycling, a calcium iron silicate structure containing manganese
are shown in Fig. 5. appeared. This could be due to the co-melting of the sludge ash and the
Based on the results, it can be seen that the synthetic gas volume perovskite OC during the continuous cycling process, resulting in the
fraction of H2 produced by CaMn0.5Fe0.5O3-δ-washed was higher than formation of a silicate structure. Additionally, diffraction peaks of Fe3O4
the other samples, reaching a maximum of about 42.5 % with a CO and Mn2O3 were observed after the reaction, suggesting that the oxygen
content of 17 %. This corresponds to over 61 % of effective fuel com­ regeneration in perovskite OC was not complete. This indicated that the
ponents. An interesting observation was the unusual finding that the uncoupled oxygen never recovered.
syngas quality was at its lowest during the initial cycle. This could be Simultaneously, to further assess the changes in the performance of
attributed to the enhanced oxygen release in the first cycle including the the OC during the multiple-cycle reaction process, the apparent
uncoupled oxygen that could not be regenerated in the next cycles, as morphology of the fresh and reacted OC was analyzed using JSM-
analyzed from the previous TGA results. The addition of cement to the 6390LV scanning electron microscope from JEOL Corporation, as
perovskite OC resulted in lower oxygen transfer, which caused the lower shown in Fig. 6 (b) and (c).
H2 content. However, this did not affect the pyrolysis and the CO content The results revealed that the crystal forms of the OC before and after
during the gasification processes, thus preserving the reactivity of the the multi-cycle reactions were rod-shaped. In case of the fresh OC, rod-
OC in the next cycles. Therefore, the syngas quality produced by the OC shaped crystal forms were relatively dispersed, most of which were well-
with cement addition was closer to that produced using CaMn0.5Fe0.5O3- defined and complete crystal structures. These forms were conducive to
δ-washed. an increase in specific surface area. Comparatively, the rod-shaped
During perovskite OC calcination, the dispersion of alkaline earth crystal forms of the OC after 5 cycles were disrupted, and the clus­
metals after washing was relatively high, effectively neutralizing the tering phenomenon was evident. The specific surface area decreased,
acidic sites of the structure and improving the stability and activity of resulting in significant attachment of the surface impurities. These
the OC to some extent. changes likely have a certain impact on the performance of the OC.
Another novel finding revealed that after multiple cycles, a hollow
structure appeared on the cross-section of some OC particles, as shown

Fig. 5. The gas content of (a) CaMn0.5Fe0.5O3-δ-washed at 3 min, (b) CaMn0.5Fe0.5O3-δ-washed at 6 min; (c) CaMn0.5Fe0.5O3-δ-washed-cement at 3 min, (d)
CaMn0.5Fe0.5O3-δ-washed-cement at 6 min.

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Fig. 6. (a)XRD curves and SEM((b) fresh;(c) reacted) of CaMn0.5Fe0.5O3-δ-washed.

in Fig. 7 (a). SEM was used to observe this hollow structure. As can be a hollow structure particle was formed with the water vapor and sodium
seen from Fig. 7 (b), there were separated substances wrapped inside the oxide steam filling the hollow space. This resulted in the increased
OC particles. It is preliminarily speculated that the foam alkali water pressure due to which the shell ruptured gradually, and the vapor was
glass solution was used to form a condensation core for the preparation released from the shell. The formation process of hollow structure is
of perovskite OC particles. During the high-temperature incineration shown in the Fig. 7 (c). Due to the reduced density of OC particles, the
process, the foam alkali underwent volume shrinkage, even co-melted hollow OC remained in the fluidized state, resulting in better contact
with some sodium salt in OC, and adhered to the OC shell. Ultimately, with the sludge particles.

Fig. 7. (a) Physical diagram;(b) SEM results and (c)cause of the formation of hollow structure of OC after multiple cycles.

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