Application Of Chemical Looping Combustion Research Articles

A phenomenological design method of the parallel packed bed reactors for chemical looping combustion of gas fuels

The parallel packed bed reactor (PPBR) is a promising route for industrial application of chemical looping combustion. This paper introduces a phenomenological approach for the rational design of PPBR, serving as a manner to efficiently obtain comprehensive design results. Based on the macroscopic propagation of heat and reaction fronts, it elucidates the dynamic heat/mass transfer within the bed. Subsequently, it is applied to design a 1.5 MWth reactor. The risk of carbon deposition in the bed is firstly investigated from a thermodynamic perspective. Then, the study reveals that the height-to-diameter ratio of the reactor must meet certain constraints to ensure stable and cost-effective operation, and these constraints are extended to the scale-up process. Sensitivity analysis is utilized to investigate the effect of key parameters on the design schemes and performance. Effects of particle size on intra-particle gas diffusion is analyzed. Finally, detailed design schemes and performance of the reactor are determined.

Gaseous alkali interactions with ilmenite, manganese oxide and calcium manganite under chemical looping combustion conditions

Alkali species present in biomass pose significant challenges in chemical looping combustion (CLC) processes and other thermal conversion applications. The interactions between different alkali species and three common oxygen carrier (OC) materials that are considered to be state of the art in CLC applications have been investigated. A dedicated fluidized bed laboratory reactor was used to study interactions of KCl, NaCl, KOH, NaOH, K2SO4 and Na2SO4 with manganese oxide, calcium manganite and ilmenite. Alkali vapor was generated by injecting alkali salts under reducing, oxidizing and inert conditions at 900 °C. Gaseous species were measured online downstream of the reactor, and the efficiency of alkali uptake was determined under different conditions. The result show significant alkali uptake by all OCs under the studied conditions. Ilmenite shows near complete alkali uptake in reducing conditions, while manganese oxide and calcium manganite exhibited less effective alkali uptake, but have advantages in terms of fuel conversion and oxidizing efficiency. Alkali chlorides, sulfates and hydroxides show distinctly different behavior, with alkali hydroxides being efficiently captured all three investigate OC materials. The findings contribute to a deeper understanding of alkali behavior and offer valuable guidance for the design and optimization of CLC with biomass.

Computational design and experimental validation of transition-metal doped CuFe2O4 as oxygen carriers in chemical-looping combustion

Owing to low cost and minimal energy penalty, chemical-looping combustion (CLC) is regarded as a promising combustion technology for fossil fuel utilization and CO2 capture. As oxygen carrier plays a key role in delivering oxygen and heat, the development of oxygen carrier with high performance is fundamental for the application of CLC. Here, a tradeoff between formation energy and transportation barrier of oxygen vacancy was found for the rational design of spinel CuFe2O4-based oxygen carriers by using a new descriptor (Φ, coupling electronegativity and atomic radius). The reactivity of CuFe2O4 is found to be strongly relevant to the proposed descriptor Φ. Compared with the undoped CuFe2O4, the formation energy and transportation barrier of oxygen vacancies in doped CuFe2O4 are reduced, which implies that oxygen migrates more easily in doped CuFe2O4. Cr and Co dopants with great potential are screened out, and they can reduce the energy barrier of CO oxidation over CuFe2O4 from 47.91 kJ/mol to 20.19 kJ/mol and 21.54 kJ/mol, respectively. Thermogravimetric analysis (TGA) experiments show that Cr dopant can improve the low-temperature reactivity of CuFe2O4, while Co dopant can facilitate the transition of CuFe2O4 to Fe3O4 and Cu (1.5CuFe2O4 + 2CO → 1.5Cu + Fe3O4 + 2CO2).

Semi-continuous Operation of Chemical Looping Combustion of Coal Using a Low-Cost Composite Oxygen Carrier

To reach the carbon peak by 2030 and achieve carbon neutrality by 2060, the implementation of low-carbon combustion approaches for fossil fuels (especially coal, a high-carbon fuel) is urgent in China. Chemical looping combustion (CLC) has been considered as one of the most promising technologies for low-carbon, efficient, and clean utilization of coal. However, a low-cost and high-performance oxygen carrier (OC) holds the bottleneck that constrains the industrial application of coal-fueled CLC. In this paper, a low-cost composite OC named Cu13.0Red87.0@C (with the mixing mass ratio of copper ore to red mud being 13.0:87.0, except for a 20 wt % cement bonder) was first prepared by the hydroforming method and then systematically evaluated by designing CLC tests in a semi-continuous fluidized bed using lignite as fuel. The results showed that this composite OC exhibited superior combustion performance in comparison to pure red mud. Moreover, it was found that increasing the temperature could significantly improve the average carbon capture efficiency but had a relatively small positive effect on the average CO2 yield. Additionally, with the elevation of the oxygen/fuel ratio, the resulting average carbon capture efficiency and average CO2 yield both tended to increase. Generally, the semi-continuous unit can simulate the continuously operated fuel reactor with an adjustable bed inventory and solid circulation rate, and it is easy to attain smooth operation of ca. 30 min, achieving both carbon capture efficiency and a CO2 yield of ca. 90%.

Recent progress in the development of synthetic oxygen carriers for chemical looping combustion applications

Continuously rising concentrations of CO2 in the atmosphere has led to significant negative impacts on the environment which propelled research efforts to replace fossil fuel-based energy with clean energy sources. However, the reliance on fossil fuel as the main energy source is projected to stay for many years to come, and therefore developing cleaner pathways to utilize fossil fuels for energy generation is paramount. Chemical looping combustion (CLC) has emerged in recent years as a promising technology for CO2 capture in power plants and other CO2 intensive industries. A key cornerstone for CLC is the development of efficient oxygen carriers with high oxygen capacity, fast kinetics, cyclic stability, mechanical strength, and low cost. The research progress in this field is rapidly growing to tackle the major materials and operational challenges to advance the knowledge toward a commercial scale CLC application. This work provides an overview of the significant advancements achieved over the past seven years in the development of synthetic metal oxide-based oxygen carriers. A summary of key performance indicators used to evaluate oxygen carriers is presented in this study to enable for a systematic assessment of the oxygen carriers’ properties and performance. This work is focused on summarizing and critically reviewing the literature on the development of oxygen carriers such as Ni, Cu, Fe, Mn, Co-based metal oxides and combined/mixed oxygen carriers in the past seven years. Studies of naturally occurring materials and waste materials used as oxygen carriers are excluded from this review which is mainly focused on synthetically prepared materials. Significant efforts were dedicated to investigating the role of the supports, synthesis methods, promotors, and other factors affecting the CLC performance of synthetic oxygen carriers using solid, liquid, and gaseous fuels. This review also outlines the main challenges, research needs and opportunities for future progress to highlight potential pathways to develop synthetic oxygen carriers in an environmentally friendly, and cost-effective manner.

Chemical looping combustion of sulfur paste to SO2 by phosphogypsum oxygen carrier for sulfur acid production

Sulfur paste is the side product of coal chemical engineering, with its main component being elemental sulfur. Sulfuric acid production via Chemical Looping Combustion (CLC) of sulfur paste is a novel technology to generate SO2 that are highly concentrated in combustion products, by means of circulating oxygen carrier particles. The objective of the present work is investigating reaction kinetics and mechanism of CLC application using sulfur paste as fuel by a phosphogypsum oxygen carrier, which is also one kind of solid waste with large stock. Thermodynamics analysis, experiments and reaction kinetics model validation were performed to evaluate the sulfur paste conversion behavior. Then, based on density functional theory and periodic structure model, the microscopic reaction mechanism of the interaction between S2 and CaSO4(010) oxygen carrier surface was studied at the molecular level. CaSO4 has the strong chemical affinity with sulfur to produce SO2, but thermodynamic limitation of S conversion to SO2 with CaSO4 oxygen carrier exits in the process. The intrinsic reduction kinetics of phosphogypsum oxygen carrier with sulfur paste focusing on the dominant reaction CaSO4 + 2S = CaS + 2SO2 was described well by the Anti-Jander function model, which agrees well with the experimental data. The formation of two SO2 molecules needs to overcome the reaction energy barrier of 124 kJ/mol.

CFD–DEM study of gas–solid flow characteristics in a fluidized bed with different diameter of coarse particles

Fluidized bed is the main reactor for the heating and gasification of coal, biomass, and other solid fuels. The diameter, density, and shape of the particles significantly affects the gas–solid​ two-phase flow process. Based on the numerical method combining computational fluid dynamics and discrete element method (CFD–DEM), this paper mainly performs numerical simulation on the gas–solid two-phase flow process of coarse particles under different inlet mass flow rates with diameters of 2.5 mm, 3.0 mm, and 3.5 mm, respectively. The high-speed photographic experiments were carried out to validate the numerical results successfully. The effects of particle diameter on bubble morphology have been compared, such as bed height and initial bed mass change rate. The maximum value of the bed height reached gradually decreases as the particle diameter increases. Two typical C-shaped bubbles were found above the large bubbles during the fluidization processes, which further improve the uniformity of mixing. Slugging appears as the width of the bubbles in the fluidized bed is close to the width of the fluidized bed, which has great effects on the mass and heat transfer. This study could serve as reference for further optimal design of fluidized bed, especially for biomass or chemical looping combustion application with coarse particles.

Application of chemical-looping combustion on waste-to-energy: A techno-economic assessment

Application of chemical-looping combustion on waste-to-energy: A techno-economic assessment

A framework for evaluating the effect of oxygen carrier characteristics on the performance of industrial-scale CLC using solid fuels

In this work we present a framework to find the potential heat recovery from Chemical Looping Combustion (CLC) using different combinations of oxygen carriers and solid fuels, based on thermodynamic equilibrium calculations. This framework requires thermodynamic information of the reacting species, which is readily available, and no kinetic information for each oxygen carrier, which is scarcer, is required. As the results of this framework are independent of the configuration of the CLC reactor, this tool can aid in the preliminary evaluation of oxygen carriers with potential for CLC applications and relevant operating conditions.

Redox performance of manganese ore in a fluidized bed thermogravimetric analyzer for chemical looping combustion

A key issue for commercial application of chemical looping combustion (CLC) technology is the selection of oxygen carriers (OCs) with good fluidization and high reactivity during the long-term redox operation. Conventional fluidized bed reactors and thermogravimetric analyzer (TGA) are fail to simultaneously satisfy the fluidization and real-time mass measurement of bed materials. A fluidized bed thermogravimetric analyzer (FB-TGA) combining the advantages of fluidized bed and TGA is believed to be a novel powerful tool for screening OCs for industrial CLC units. In this work, an innovative FB-TGA with a high weight measurement accuracy is designed to reflect the lifetime, redox reactivity, particle sintering and agglomeration characteristics of OCs during the CLC. Manganese ore was selected as a representative OC and redox cyclic tests with hydrogen as the reduction gas were conducted. Results indicate that the Mn3O4-MnO system acts as the main redox pair. The redox chemical reactions may intensify the attrition of manganese ore particles. This may be due to the pore-opening effect of H2 during the reduction of manganese ore, reducing mechanical strength and accelerating attrition of particles. In the reducing atmosphere, it is speculated that the generation of manganese silicates with a low melting point results in particle sintering and agglomeration at the bottom of the bed. The particle agglomeration gradually spreads inward and upward, and eventually leads to total collapse of the fluidized bed. Therefore, a high-grade manganese ore with less silicon element is more suitable for industrial CLC pilots.

Reaction characteristics investigation of CeO2-enhanced CaSO4 oxygen carrier with lignite

Calcium sulfate (CaSO4) has been verified as a promising oxygen carrier (OC) in the chemical looping combustion (CLC) for its high oxygen capacity, abundant reserve and low cost, but its low reactivity and deleterious sulfur species emission from the side reactions of CaSO4 should be well considered for its wide application in CLC. In order to promote the reactivity of CaSO4 and increase its potential to inhibit the gaseous sulfur emission, a CeO2-enhanced CaSO4 OC mixed OC of core–shell structure was prepared using the combined template synthesis method. Reaction characteristics of the prepared CaSO4-CeO2 mixed OC with a typical lignite was first conducted and systematically investigated, and an improved reactivity of the prepared CaSO4-CeO2 mixed OC was demonstrated than its single component CaSO4 or CeO2 due to the fast transfer and exchange of oxygen from the CaSO4 substrate to coal via the doped CeO2. Furthermore, the solid products formed from the mixed CaSO4-CeO2 OC with the selected coal were collected and analyzed. Especially, evolution and redistribution of the sulfur species of different forms were focused. At the latter reaction stage of YN reaction with the CaSO4-CeO2 mixed OC, the SO2 emitted from the side reactions of CaSO4 was greatly diminished and the doped CeO2 was proven effective to directionally fix the SO2 released to turn into different solid sulfur compounds, which were determined as Ce2O2S, Ce2S3 and Ce2(SO4)3·5H2O and formed through the different pathways. In addition, good regeneration of the reduced CaSO4-CeO2 mixed OC could be reached in spite of the unavoidable interaction between the included minerals in coal and the reduced mixed OC. Overall, the combined template method-made CaSO4-CeO2 mixed OC reported herein was not only endowed with enhanced reactivity for coal conversion, but also owned the potential to directionally fix the gaseous sulfur emission, which is quite applicable as OC for simultaneous decarbonatization and desulfurization in the real CLC process.

Oxygen carriers from incineration bottom ash for chemical looping combustion of syngas: Effect of composition on combustion efficiency

Incineration bottom ashes (IBA) were investigated as oxygen carriers (OCs) for their application in chemical looping combustion (CLC). The OCs were prepared by mixing the magnetic separated fraction of IBA (IMF) with its non-magnetic fraction (NMF) at various ratios. Additionally, a synthesized iron oxide supported on the pre-washed IBA (0, 25, 50 and 75 wt%), termed as synFe, were also investigated for comparison with the investigated IMF. Thermogravimetric analysis (TGA) combined with elemental analysis unveiled that Fe2O3 and CaSO4 in IMFs were the major sources of the available lattice oxygen in the investigated oxygen carriers. A synergistic effect was observed among the complex components in IMF-based OCs causing the experimental oxygen transport capacity to be larger than the theoretically expected, calculated based on the metal oxides (including Fe2O3, CuO, Mn2O3 and NiO) and CaSO4 redox couples. A syngas (H2 + CO) combustion tests with the IMF-based OCs in a bench-scale fluidized bed reactor were conducted, where the100-IMF demonstrated the most pronounced and stable combustion performance (95% for H2 and 90% for CO), comparable to those delivered by 50% and 75% synFe. Based on this study, the IMF compounds from the raw IBA without any further treatment carry a high potential for CLC process, which provides possible option of a cost-effective OCs and sustainable application of IBA.

Petroleum coke conversion behavior in catalyst-assisted chemical looping combustion

Efficiently using petroleum coke as fuel and reducing carbon emission meanwhile have become attractive in oil processing industry. The paper is focused on the application of Chemical Looping Combustion (CLC) with petroleum coke, with the purpose of investigating its combustion performance and effects of potassium. Some experiments were performed in a laboratory scale fluidized bed facility with a natural manganese-based oxygen carrier. Experimental results indicated that the coke conversion is very sensitive to reaction temperature. The present natural manganese-based oxygen carrier decorated by K has little effect on the improvement of coke conversion. XRD, SEM–EDX, and H 2 -TPR were adopted to characterize the reacted oxygen carrier samples. After being decorated by K, the oxygen carrier's capacity of transferring oxygen was decreased. A calcination temperature above the melting point of K 2 CO 3 (891 °C) shows better oxygen transfer reactivity in comparison to the one calcined at a lower temperature. The natural oxygen carrier used in the work has a high content of Si, which can easily react with K to form K(FeSi 2 O 6 ). Further, irrespective of reaction temperature, the coke conversion can be significantly enhanced by decorating the coke with K, with a demonstration of remarkably shorter reaction time, faster average coke gasification rate and higher average carbon conversion rate.

Progress in the CO2 Capture Technologies for Fluid Catalytic Cracking (FCC) Units—A Review

© Copyright © 2020 Gulec, Meredith and Snape. Heavy industries including cement, iron and steel, oil refining, and petrochemicals are collectively responsible for about 22% of global CO2 emissions. Among these industries, oil refineries account for 4–6%, of which typically 25–35% arise from the regenerators in Fluid Catalytic Cracking (FCC) units. This article reviews the progress in applying CO2 capture technologies to FCC units. Post combustion and oxyfuel combustion have been investigated to mitigate CO2 emissions in FCC and, more recently, Chemical Looping Combustion (CLC) has received attention. Post combustion capture can readily be deployed to the flue gas in FCC units and oxyfuel combustion, which requires air separation has been investigated in a pilot-scale unit by Petrobras (Brazil). However, in comparison, CLC offers considerably lower energy penalties. The applicability of CLC for FCC has also been experimentally investigated at a lab-scale. As a result, the studies demonstrated highly promising CO2 capture capacities for FCC with the application of post combustion (85–90%), oxyfuel combustion (90–100%) and CLC (90–96%). Therefore, the method having lowest energy penalty and CO2 avoided cost is highly important for the next generation of FCC units to optimize CO2 capture. The energy penalty was calculated as 3.1–4.2 GJ/t CO2 with an avoiding cost of 75–110 €/t CO2 for the application of post combustion capture to FCC. However, the application of oxyfuel combustion provided lower energy penalty of 1.8–2.5 GJ/t CO2, and lower CO2 avoided cost of 55–85 €/t CO2. More recently, lab-scale experiments demonstrated that the application of CLC to FCC demonstrate significant progress with an indicative much lower energy penalty of ca. 0.2 GJ/t CO2.

Effect of calcination condition on the performance of iron ore in chemical-looping combustion

The calcination of oxygen carrier is the essential step prior to its application in chemical looping combustion, which is significantly influenced by calcination conditions. In this study, a natural iron ore was treated under the combined effect of three key calcination parameters (heating rate, temperature, and duration time). The reactivity performance of calcined iron ores was evaluated with CO as fuel, and the iron ore with the best performance and the parameter with the greatest impact were screened. The results showed that the iron ores treated under different calcination conditions showed evident difference in their reactivity, in which calcination temperature showed the biggest impact on the physicochemical properties of fresh iron ore. The best calcined iron ore was obtained under the heating rate of 15 °C/min, the temperature of 1050 °C, and the duration time of 60 min within the selection limits of three calcination parameters, and its cyclic test showed that the maintained good physical structure of best calcined iron ore guaranteed it against the reactivity decay, a stable recyclability performance was achieved during the consecutive redox cycles. The findings in this study could provide a reference for the further optimization of calcination parameters suitable for commercial oxygen carriers.

Synergy of red mud oxygen carrier with MgO and NiO for enhanced chemical-looping combustion

Low-cost oxygen carriers prepared by natural ores or solid wastes have been attracted much attention for large-scale application in chemical looping combustion (CLC) technology. However, these oxygen carriers usually exhibit low activity and poor stability because of their unsatisfied microstructure and/or components. In this study, red mud as oxygen carrier was modified by active (NiO or MnOx) and inert oxides (MgO, Al2O3 or ZrO2) to optimize its structure and composition for CLC of methane. The synergy among different components in the oxygen carriers for methane oxidation was discussed in detail. The results showed that the effect of MnOx on the reducibility of red mud was relatively weak, while the presence of a suitable amount of NiO significantly promoted the reactivity for methane complete oxidation. Addition of 15 wt% NiO could increase the average CH4 conversion and CO2 selectivity from 53% to 65%–75% and 99%, respectively, which is beneficial for the following capture of CO2 after combustion. Moreover, the addition of MgO into the NiO-RM carrier could improve the stability of oxygen carrier for successive chemical looping process. The formation of NiFe2O4 and MgNiO2 in the oxygen carrier contributed to the enhanced reducibility, and the multiple interactions among Fe, Ni and Mg oxides promoted the overall performance of oxygen carriers. During the reaction with methane, Ni oxides were firstly reduced to metal Ni, which acted as a catalyst to activate methane, improving the oxidation rate of methane by oxygen carriers.

A novel air reactor concept for chemical looping combustion systems operated at high pressure

We analyse the viability of a novel reactor concept for chemical looping combustion applications with CO2 capture. The reactor consists of a packed bed of reduced oxygen carrier particles traversed by a series of empty conducts oriented in the axial direction. These conducts are made of permeable but non-selective porous walls, through which air diffuses towards the region of reacting solids. The diffusion flux of air through the orifices, which is perpendicular to the main bulk flow of gas along the conducts, imposes very long oxidation times for all the reacting particles and a quasi-steady heating up of the air flow. The conducts designed to have a very high length/diameter ratio (i.e. above 50) allow a large bypass of pressurized air through the reactor without coming into direct contact with the solids, resulting in a modest pressure drop of the gas (i.e. below 5% at the reactor exit). A preliminary reactor design example is described for a case using Fe/Fe2O3 pellets as oxygen carrier, which are packed into a reactor (L = 100 m, I.D. = 2 m) traversed by air conducts (I.D. = 0.05 m) with a wall 2 mm thick and orifices occupying an area fraction of 0.12. The reactor can initially generate 100 MWth, with a gas flow at the exit at close to 1050 °C and 19 atm, and it could be used intermittently for more than 9 h as the main heater in a highly efficient Brayton cycle.

Interaction of manganese with aluminosilicate support during high temperature (1100 °C) chemical looping combustion of the Fe-Mn-based oxygen carrier

Investigation of the redox reactivity of mixed-metal oxides in Chemical-Looping Combustion (CLC) can improve our understanding of the associated reaction mechanisms that are related to this technology. The Fe-Mn-based oxygen carrier supported on a spent fluid catalytic cracking catalyst (FCC) was characterized during CLC of CH4 by fixed bed reactor studies coupled with mass spectrometry, X-ray diffraction, and Raman spectroscopic analysis. Research was carried out to investigate Mn interaction with the FCC support during the high temperature (1100 °C) CLC and the potential impact on performance. The addition of Mn to Fe/FCC led to an increase in the oxygen transfer capacity at 900 °C and a decrease in oxygen transfer capacity at 1100 °C. Following 15 redox cycles, the average methane conversion was 85% at 900 °C and 68% at 1100 °C. The Fe-Mn/FCC carriers were selective for CO2 at 900 °C, and selective for CO at 1100 °C, which is consistent with the thermodynamic limitation of CO2 production at high-temperature. The Fe-Mn/FCC oxygen carrier’s crystal structure remained stable at 900 °C, whereas at 1100 °C, XRD and Raman spectroscopic analysis revealed formation of MnAl2O4 and Al2Mn3Si3O12 phases due to reduced Mn metal alloying with the aluminosilicate. The decrease in reactivity and oxygen transfer capacity at 1100 °C was attributed to the formation of new Fe-Mn phases and alloying with the aluminosilicate, sintering, and agglomeration at high-temperature. These results demonstrate the need to stabilize the Mn-active phase of oxygen carriers on aluminosilicate supports being used for the high-temperature CLC application.

Numerical Investigation of Solid-Fueled Chemical Looping Combustion Process Utilizing Char for Carbon Capture

The in-depth understanding of the gas–solid flow and reaction behaviors, and their coupling characteristics during the chemical looping combustion (CLC) process has the guiding significance for the operation and optimization of a chemical looping combustor. A three-dimensional numerical model is applied to investigate the char-fueled CLC characteristics in a fuel reactor for efficient CO2 separation and capture. Simulations are carried out in a bubbling fluidized bed fuel reactor with a height of 2.0 m and a diameter of 0.22 m. The initial bed height is 1.1 m, and hence the height–diameter ratio of the slumped bed is five. The oxygen carrier is prepared with 14 wt% of CuO on 86 wt% of inert Al2O3. In the process of mathematical modeling, a Eulerian-Eulerian two-fluid model is adopted for both of the gas and solid phases. Gas turbulence is modeled on the basis of a k–ε turbulent model. The reaction kinetics parameters are addressed based upon previous experimental investigations from literature. During the simulation, the gas–solid flow patterns, composition distributions, and reaction characteristics are obtained. Moreover, the effects of solids inventory and fluidizing number on the reaction performance are elucidated in-depth. The results have shown that the reaction rates have close relationship with the flow patterns and the distributions of gas concentrations. Compared to the steam-char gasification over sand, the application of char-fueled CLC can effectively promote the conversion of gasification products. In addition, higher CO2 concentration at the outlet can be achieved by increasing the initial solids inventory or decreasing the fluidizing number. Some calculated values are verified by the previous data, indicating that the current three-dimensional models are reasonable to study the process mechanism of char-fueled CLC.

Ice-Templated Geopolymer—Fe/Mn Oxide Composites Conceived as Oxygen Carriers

Ice-templating (freeze-casting) technique was applied to a novel class of geopolymer composites containing Fe/Mn oxides, previously tested and reported in others works as synthetic oxygen carriers for chemical looping combustion (CLC), in order to obtain composite monoliths with lamellar macro-porosities by unidirectional freezing of water-based sol-gel systems. Geopolymer-Fe/Mn oxides composites carriers were also produced as beads, suitable for fixed bed reactors, by an injection-solidification method in liquid nitrogen. After conditioning at 900 °C, the temperature needed for CLC applications, the composite beads and monoliths possess similar total porosity % and total pore volume, being ≈65% and 570 mm3 g−1, respectively, as well as a specific surface area of around 2.4–2.9 m2/g.