Sorption-enhanced Reforming Research Articles

A thermodynamic comparison of membrane-assisted processes for hydrogen production with integrated CO2 capture

The energy efficiency of two novel process designs for the production of ultra-pure hydrogen with simultaneous capture of CO2 using CH4 as the feedstock, namely membrane-assisted chemical looping reforming (MA-CLR) and membrane-assisted sorption-enhanced reforming (MA-SER) has been compared. The modelling of the integrated network for mass and heat balances has been carried out using the ASPEN® Plus V10 process simulation tool to quantify the benefits and disadvantages of integrating hydrogen perm-selective membranes with either chemical looping or sorption-enhanced reforming. The evaluation of the MA-CLR process is carried out for a range of the following operating conditions: 10 < pR < 60 bar, 500 < TR < 900°C, and 1.5 < H2O/CH4 < 3.0. On the other hand, for the MA-SER process the operation ranges of 1.0 < pR < 10 bar, 400 < TR < 900°C, and 2.5 < H2O/CH4 < 4.0 were considered. Within the operation window of the MA-SER process, no carbon formation is observed, as any carbon present in the system reacts with CaO in the form of CO2. However, in the case of the MA-CLR process, carbon formation can occur during the pre-reforming stage, particularly at low H2O/CH4 ratios. In terms of hydrogen yield, energy utilization and carbon capture, the MA-CLR outperforms the MA-SER plant. However, the MA-SER plant offers certain advantages over the MA-CLR system, such as a pure CO2 product stream and lower reactor design temperatures. In the MA-CLR system, a carbon capture rate of 99.8% and a hydrogen product yield of 74.4% are achieved, whereas the MA-SER plant achieves a carbon capture rate of 98.5% and a hydrogen product yield of 69.7%.

Ni alumina-based catalyst for sorption enhanced reforming - Effect of calcination temperature

Effect of calcination temperature (350 °C – 850 °C) on the physicochemical properties as well as catalytic performance of Ni-based catalyst for the hydrogen production via steam methane reforming (SMR) and sorption enhanced reforming (SER) has been investigated. Catalyst calcined at highest temperature (850 °C) shows formation of NiAl2O4 confirmed by XRD. Consequently, a much higher reduction temperature (875 °C) is required to reduce this Ni aluminate spinel to an active Ni catalyst. Catalyst calcined at highest temperature (850 °C) showed much higher CH4 conversion and H2 production in SMR compared to the catalysts calcined at lower temperatures. In addition, higher CH4 conversion and H2 production was observed for the 15%Ni/alumina_850 catalyst after aging (long exposure to steam and high temperature) compared to commercial reforming catalyst. Finally, a much better stability is observed for the 15%Ni/alumina_850 catalyst compared to the commercial reforming catalyst after 100 SER/regeneration cycles under relevant reaction conditions. The formation of NiAl2O4 during high temperature calcination plays a vital role in the robustness and stability of the Ni-based catalysts and can be useful synthesis procedure for increasing the catalyst lifetime.

Sorption-enhanced reforming of raw COG and its adaptability to hydrogen metallurgy: Thermodynamic analysis

In order to solve the problem of hydrogen shortage in the popularization of hydrogen metallurgy, the steam reforming of raw coke oven gas (raw COG) and its adaptability in reducing sinter ore were studied thermodynamically in this paper. Compared to the self-reforming and steam reforming, the maximum of hydrogen yield in the sorption-enhanced reforming process can go up to 1.54 mol/mol raw COG and move the reforming temperature from above 900 °C to the zone between 500 °C and 600 °C. According to the concentrations of reducing gas components to be used in the hydrogen metallurgy, the reformed gases from raw COG was merged and rearranged, and then six kinds of reformed gases were selected as typical gases for the subsequent reduction of sinter ore. The reformed gas can effectively reduce the formation of the intermediate product and improve the yield of iron, and the temperature requirement of the reduction process was reduced. Finally, based on a comprehensive analysis of the raw material consumption for the reforming and reduction processes, the optimal reforming condition that reforming temperature is 500 °C, S/C (the molar ratio of steam to carbon) is 3.6 and CaO/C (the molar ratio of CaO to carbon) is 2.0 and the optimal reduction condition that reduction temperature is 900 °C–1100 °C, R/O ratio is 2.0 are obtained. The matched optimization leads to a reduction in both RCOG and sinter consumptions, significantly reducing the consumption of raw materials and improving the economy of the hydrogen metallurgical process.

Hydrogen production from biomass via moving bed sorption-enhanced reforming: Kinetic modeling and process simulation

This study explored a process intensification approach for hydrogen production through biomass gasification. Sorption-enhanced reforming (SER) in an autothermal countercurrent moving bed reformer is proposed as an alternative to multiple units traditionally required for syngas conditioning. This process utilizes the selective sorption and catalytic properties of calcium oxide to integrate multiple reforming reactions into a moving bed reactor. A multistage kinetic model was used to analyze and optimize the key operating parameters of the reformer. Results showed that the moving bed reformer completely converts all tars and increases the hydrogen concentration of syngas from 23 mol% to 80 mol% (dry basis). A comparison between equally sized models showed that the moving bed reformer outperforms a fluidized bed reformer under similar conditions. Simulation of the entire process showed that the hydrogen yield of the proposed SER process is 5% higher than the conventional process. In addition, the proposed process produces surplus electricity, while the conventional process has a 26% power deficit. The overall efficiency of the proposed process is 3.5% higher than the conventional process. The improved process efficiency, coupled with the potentially lower costs of a streamlined process, indicates that the proposed process is a promising route for green hydrogen production.

Modelling of methane sorption enhanced reforming for blue hydrogen production in an adiabatic fixed bed reactor: unravelling the role of the reactor's thermal behavior

Methane sorption enhanced reforming (SER) is investigated in this work as a promising route for blue H2 production. A 1-D dynamic heterogeneous model is developed to evaluate the thermal behavior of a fixed bed reactor under adiabatic conditions. The heterogeneous model allows to decouple the feed gas temperature from the initial solid one in order to investigate the behavior of the reforming step in a temperature swing reforming/regeneration process. The effects of the feed gas temperature, the initial bed temperature, and the bed thermal capacity are studied by evaluating the global impact of each parameter through a set of key performance indices (CH4 conversion, H2 yield and purity, carbon capture ratio) calculated as integrals over the duration of the reforming step. The results highlight the minor effect of the initial bed temperature on the process performances showing the potential of minimizing the extent of a cooling step between regeneration and reforming stages. Besides, due to the endothermic nature of the methane sorption enhanced reforming process at high temperatures, thermal energy must be provided to the SER process to achieve high CH4 conversion and high carbon capture ratio. This can be made either in the form of high feed temperature or by utilizing the energy stored in the bed benefiting from the bed thermal capacity.

Environmental evaluation of hydrogen production employing innovative chemical looping technologies – A Romanian case study

A cradle-to-gate life cycle assessment is carried out to evaluate the environmental impact of producing 1 kg of hydrogen implementing innovative chemical looping technologies: chemical looping hydrogen production (CLH), sorption enhanced reforming (SER), and sorption enhanced chemical looping reforming (SECLR). The performance of the looping technologies is compared against conventional hydrogen production without and with CO2 capture, as well as against green hydrogen production in order to determine the more environmentally-friendly option. Comparing the looping technologies with the reference blue hydrogen production it shows that CLH has a lower environmental burden, presenting smaller values in 9 out of 12 environmental impact indicators. If we confront the looping technologies against each other, CLH shows better performance in 11 out of 12 environmental indicators. As expected, green hydrogen has a much smaller overall environmental impact with the exception of human toxicity, terrestrial ecotoxicity and mineral depletion.

Techno-economic assessment of a chemical looping splitting system for H2 and CO Co-generation

The natural gas (NG) reforming is currently one of the low-cost methods for hydrogen production. However, the mixture of H2 and CO2 in the produced gas inevitably includes CO2 and necessitates the costly CO2 separation. In this work, a novel double chemical looping involving both combustion (CLC) and sorption-enhanced reforming (SE-CLR) was proposed towards the co-production of H2 and CO (CLC-SECLRHC) in two separated streams. CLC provides reactant CO2 and energy to feed SECLRHC, which generates hydrogen in a higher purity, as well as the calcium cycle to generate CO in a higher purity. Techno-economic assessment of the proposed system was conducted to evaluate its efficiency and economic competitiveness. Studies revealed that the optimal molar ratios of oxygen carrier (OC)/NG and steam/NG for reforming were recommended to be 1.7 and 1.0, respectively. The heat integration within CLC and SECLRHC units can be achieved by circulating hot OCs. The desired temperatures of fuel reactor (FR) and reforming reactor (RR) should be 850 °C and 600 °C, respectively. The heat coupling between CLC and SECLRHC units can be realized via a jacket-type reactor, and the NG split ratio for reforming and combustion was 0.53:0.47. Under the optimal conditions, the H2 purity, the H2 yield and the CH4 conversion efficiency were 98.76%, 2.31 mol mol−1 and 97.96%, respectively. The carbon and hydrogen utilization efficiency respectively were 58.60% and 72.45% in terms of the total hydrogen in both steam and NG. The exergy efficiency of the overall process reached 70.28%. In terms of the conventional plant capacity (75 × 103 t y−1) and current raw materials price (2500 $ t−1), the payback period can be 6.2 years and the IRR would be 11.5, demonstrating an economically feasible and risk resistant capability.

Bi-Functional Catalyst/Sorbent for a H2-Rich Gas from Biomass Gasification

The aim of this work is to identify the effect of the CaO phase as a CO2 sorbent and mayenite (Ca12Al14O33) as a stabilizing phase in a bi-functional material for CO2 capture in biomass syngas conditioning and cleaning at high temperature. The effect of different CaO weight contents is studied (0, 56, 85, 100 wt%) in sorbents synthesized by the wet mixing method. These high temperature solid sorbents are upgraded to bi-functional compounds by the addition of 3 or 6 wt% of nickel chosen as the metal active phase. N2 adsorption, X-ray diffraction, scanning electronic microscopy, temperature-programmed reduction analyses and CO2 sorption study were performed to characterize structural, textural, reducibility and sorption properties of bi-functional materials. Finally, sorption-enhanced reforming of toluene (chosen as tar model), of methane then of methane and toluene with bi-functional compounds were performed to study the best material to improve H2 content in a syngas, provided by steam biomass gasification. If the catalytic activity on the sorption enhanced reforming of methane exhibits a fast fall-down after 10–15 min of experimental test, the reforming of toluene reaches a constant conversion of 99.9% by using bi-functional materials.

Combined autothermal and sorption-enhanced reforming of olive mill wastewater for the production of hydrogen: Thermally neutral conditions analysis

A thermodynamic study and an energy analysis are performed on the autothermal reforming (ATR) and sorption-enhanced autothermal reforming (SE-ATR) of olive mill wastewater (OMW) to produce green hydrogen. For comparative purposes, the traditional reforming (TR) and sorption-enhanced reforming (SER) are also assessed. The thermodynamic equilibrium compositions are calculated by using the Gibbs free energy minimization method. The effect of temperature, pressure and steam-to-carbon molar ratio (S/C) is assessed for the different reactor configurations. The energy analysis is done by determining the level of oxygen needed to operate under thermally neutral conditions.The results show a reduced hydrogen yield for ATR and SE-ATR compared to their non-autothermal counterparts, but a decreased energy requirement per mole of hydrogen produced. For the ATR, the thermally neutral operation requires a high amount of oxygen, which reduces the hydrogen yield. However, for SE-ATR, the exothermal sorption reaction provides nearly enough energy for the process to be thermally neutral by itself.

Hydrogen production through chemical looping and sorption-enhanced reforming of olive mill wastewater: Thermodynamic and energy efficiency analysis

A thermodynamic study was performed aiming to compare the performance of different reactor configurations, namely traditional (TR), sorption-enhanced (SER), chemical looping (CLR) and chemical-looping sorption-enhanced reforming (SE-CLR) for the steam reforming of olive mill wastewater (OMW), a byproduct of olive oil production, to produce green hydrogen. This analysis was accompanied by an energy balance in order to maximize energy efficiency and achieve autothermal operating conditions. The parameters assessed in the thermodynamic study were temperature (250–900 °C) and steam-to-carbon molar ratio (0.15–3.0), but also, for the sorption-enhanced process, the ratio between the CO2 sorbent and the OMW (0–8.0), and for the chemical looping process the ratio between the oxygen carrier and the OMW (0–6.0). The SER showed higher hydrogen yield for the range of conditions tested than both the traditional and chemical looping reformers, with a hydrogen purity above 99%. By combining sorption-enhanced with chemical looping reforming, an H2 purity above 99% and a yield higher than that for chemical looping by itself were observed. For the CLR and SE-CLR configurations, a system in which the energy released is higher than the required was achieved by varying the amount of oxygen carrier, enabling operating under autothermal conditions. A pinch analysis was performed for the CLR and the SE-CLR to quantify the possible heat integration in a realistic system. It was found that CLR can be 71% self-sufficient, whilst SE-CLR can be 55% self-sufficient.

Model validation of the Ca-Cu looping process

In this work an experimental demonstration and validation of a 1-D pseudo homogeneous reactor model for the Ca-Cu looping process is presented. The Ca-Cu looping process is a highly integrated process based on sorption-enhanced reforming of methane using CaO as sorbent, combined with chemical looping of a Cu-based oxygen carrier to provide the energy for the regeneration of the sorbent. Experiments were carried for all three involved process steps. The sorption-enhanced reforming step was studied at two different scales under different conditions. The effects of different bed compositions, operating temperatures, methane residence times and different steam-to-carbon ratios on the hydrogen production rate have been evaluated. A methane space velocity of 2.26 kgCH4h−1 kgcat−1 and a temperature range of 600–650 °C were found to be the most appropriate for optimal performance of the SER step and when increasing the steam-to-carbon ratio the hydrogen fraction produced increased.Moreover, complete cycles (consecutive steps of sorption-enhanced steam reforming, oxidation and reduction/calcination) have been performed in a medium-scale packed bed reactor (0.6 m length), where the three functional materials needed for this process were physically mixed. The Ca-Cu process was successfully demonstrated experimentally, forming 90% of H2 in the sorption enhanced reforming stage and regenerating well the sorbent in the reduction/calcination step.The experimental results obtained from the experimental campaign have been used to validate a packed bed reactor model and a good agreement between the model and the experimental data was found.

Decarbonizing cement plants via a fully integrated calcium looping-molten carbonate fuel cell process: Assessment of a model for fuel cell performance predictions under different operating conditions

This study is part of a comprehensive research devoted to the integration of a Calcium Looping (CaL) process with a Molten Carbonate Fuel Cell (MCFC) for the decarbonisation of a full-scale cement plant. In the proposed process, where the energy intensive oxy-combustion occurring in the CaL calciner is replaced with a conventional combustion in air. The CO2-rich gas leaving the calciner is injected into the MCFC cathode while the anode side is fuelled by H2-rich gases produced by a sorption-enhanced reforming (SER) process. The high CO2-concentrated gas leaving the anode will be sent to valorisation processes and/or the CO2 final disposal.Here we focus on modelling, simulation and characterization of the MCFC used as a device for CO2 separation as well as electricity production, here considered as a process by-product. Polarization curves (I–V curves) and Electrochemical Impedance Spectroscopy (EIS) were measured to support the development and the calibration of a semi-empirical model obtained by theoretical consideration.The experimental campaign demonstrated that the fitted model is able to reproduce the real cell performance when varying the temperature, H2 concentration, CO2 concentration at anode and cathode respectively as well as CO2 CaL capture rate.Indeed, the average difference between numerical and experimental results is always below 2%.Results also demonstrated that the MCFC can be usefully considered as an efficient CO2 concentrator, with a CO2 fraction at the anode outlet that is greater than 51% on a dry basis.

Understanding the effect of H2S on the capture of CO2 using K-doped Li4SiO4 sorbent

Li4SiO4 is a well-acknowledged CO2 sorbent in the sorption-enhanced reforming system for low-cost H2 production with a high purity. However, the inevitable presence of H2S in the biomass-derived syngas etc. could possibly affect the in-situ CO2 adsorption significantly, which is important but has never been reported. In this work, the adsorption of CO2 using Li4SiO4 was investigated under varying H2S concentrations and reaction temperatures, and a series of characterization techniques were utilized to understand the effect of H2S and its action mechanism. The results show that the presence of H2S causes a rapid loss-in-capacity of Li4SiO4 in capturing CO2 during the cyclic reactions, and a higher concentration greatly exacerbates the problem. Moreover, the negative impact of H2S is found to have a strong relationship to the reaction temperature. It is proposed that at 325~475 °C, Li4SiO4 and H2S react to form bits of Li2S and some kinds of sulfates, and at 625~775 °C, a large amount of dense KLiSO4 is generated covering the surface of the sorbent. In contrast, at a high temperature above 925 °C, sintering of Li4SiO4 plays a critical role, leading to a significant change on its microstructure.

CaCO3 decomposition for calcium-looping applications: Kinetic modeling in a fixed-bed reactor

Calcium looping can be used in various environmental applications such as post-combustion CO2 capture, sorption-enhanced reforming and thermochemical energy storage. The calcination reaction mechanism and the effect of CO2 partial pressure have not been fully clarified yet justifying further efforts; this work focuses on kinetic modeling of the reaction. Herein, calcination kinetics of limestone were studied experimentally in a fixed-bed reactor, and theoretically using different models previously reported in the literature. The Uniform Conversion Model (UCM) and the Changing Grain Model (CGM) described better the conversion-time data than the Random Pore Model (RPM). A Langmuir-Hinshelwood mechanistic model, which included the decomposition of CaCO3, the desorption of CO2 and the CaO* relaxation fitted well the reaction rate values leading to an activation energy of 210 kJ/mol and the pre-exponential factor equal to 18,860 kmol/(m2 s). The model was validated by predicting adequately the decomposition rates measured by other authors under different conditions.

Ca-Mg-Al-oxide Sorbents Prepared from Hydrotalcite Precursors for CO2 Capture at Realistic Calcium Looping Conditions

The calcium looping (CaL) process, based on the cyclic carbonation/calcination of CaO sorbents, has been widely investigated recently as a potential technique to capture CO2 at reduced energy penalty. This process can be used in facilities such as power plants and produce a concentrated CO2 which is suitable for storage. In recent years, the hydrogen production processes become more important due to the development of sustainable energy. The CaL process can also be combined with reforming process to produce a concentrated stream of H2 >98 vol. % in a single step, which is known as sorption-enhanced reforming (SER) process, reducing the cost of H2 production effectively. The capture capacities and multicycle stabilities of sorbents are crucial in these uses. In this study, a series of CaMgAl oxide materials for CO2 capture, derived from layered-double hydroxides (LDHs), were prepared to test their performances at realistic calcium looping conditions, namely at high CO2 concentration in the calcination stage. A series of materials with different CaMgAl molar ratios were tested at different regeneration temperatures, regeneration times, and in different CO2 concentrations at the regeneration stage to find out the optimal treatment conditions. The multicycle capture capacities of these materials were examined and compared with that of limestone. Materials regenerated for 15 minutes at 930°C and 70∼100% CO2 had good performances. The Ca/Al = 7/1 materials possessed well capture capacity and multicycle stability compared with that of limestone. Addition of magnesium oxide can further improve its performance. In the 40 cycles test, although the initial capture capacity of the CaMgAl material was lower than that of the CaAl materials, because of the better stability of the former, its capture performance was better than that of the CaAl material at the end of the loop. These materials have the potential to be applied in hydrogen production and other related processes in the future.

Techno-economic assessment of hydrogen production processes based on various natural gas chemical looping systems with carbon capture

Hydrogen is regarded as a promising energy carrier with several key advantages for future low carbon applications (e.g. no greenhouse gas emission at the point of use, higher energy conversion efficiency). This paper is assessing from a techno-economic point of view, three chemical looping processes suitable for hydrogen production generating high purity hydrogen corresponding to 300 MW thermal output, with a carbon capture rate of at least 90%: i) chemical looping hydrogen production (CLH), ii) sorption enhanced reforming (SER), iii) sorption enhanced chemical-looping reforming (SECLR). Key techno-economic performance indicators were evaluated and compared amongst each other and against a conventional natural gas reforming technology without/with carbon capture by chemical gas-liquid absorption using alkanolamines. The results show that CLH using iron-based (i.e. ilmenite) oxygen carrier seems to be the most promising hydrogen production technology amongst the evaluated systems having the highest energy efficiency at CCR>99%, lower operating and maintenance (O&M) costs, with a hydrogen production cost of 41.84 €/MWh compared to 42.43 €/MWh for no capture conventional reforming and 44.58 €/MWh for amine-based capture with 70% CCR, at a CO2 emissions avoidance cost of 19.46 €/tCO2.

Performance and operating limits of a sorbent-catalyst system for sorption-enhanced reforming (SER) in a fluidized bed reactor

The combined performance of a synthetic CaO-Ca12Al14O33 sorbent and an Ni-MgAl2O4 reforming catalyst was tested in a fluidized bed reactor under relevant operating conditions for the sorption-enhanced reforming (SER) process. The effect of CH4 space velocity (i.e. kgCH4/h·kgcat), steam-to-carbon (S/C) ratio and superficial gas velocity on product gas composition was assessed, as well as the effect of regeneration conditions on material performance. Moreover, a bi-functional material prepared by mechanical mixing of the separate materials was also tested in the reactor under consecutive SER/regeneration cycles. H2 contents as high as 96 vol% (N2 free, dry basis) were achieved under SER operation, using the separate materials working with an Ni content of 3.75 wt% in the solid bed at 650 °C with S/C ratios of 3 and 4. This solid system is able to process up to 0.63 kgCH4/h·kgcat at 0.1 m/s superficial gas velocity and with an S/C ratio of 4, although the CH4 input has to be reduced to 0.33 kgCH4/h·kgcat when working with a lower S/C ratio. Similar H2 contents to those found with the separate materials were obtained with the combined sorbent-catalyst material working with 0.33 kgCH4/h·kgcat at 0.1 m/s superficial gas velocity and S/C ratios of 3 and 4. The CO2 sorption capacity of the combined material produced the same as that of the separate sorbent particles (i.e. around 0.25 gCO2/g calcined sorbent), while remaining stable throughout the SER/regeneration cycles.

Performance of Li₄SiO₄ Material for CO₂ Capture: A Review.

Lithium silicate (Li4SiO4) material can be applied for CO2 capture in energy production processes, such as hydrogen plants, based on sorption-enhanced reforming and fossil fuel-fired power plants, which has attracted research interests of many researchers. However, CO2 absorption performance of Li4SiO4 material prepared by the traditional solid-state reaction method is unsatisfactory during the absorption/regeneration cycles. Improving CO2 absorption capacity and cyclic stability of Li4SiO4 material is a research highlight during the energy production processes. The state-of-the-art kinetic and quantum mechanical studies on the preparation and CO2 absorption process of Li4SiO4 material are summarized, and the recent studies on the effects of preparation methods, dopants, and operating conditions on CO2 absorption performance of Li4SiO4 material are reviewed. Additionally, potential research thoughts and trends are also suggested.

Combined sorbent and catalyst material for sorption enhanced reforming of methane under cyclic regeneration in presence of H2O and CO2

An investigation on an innovative calcium‑nickel Combined Sorbent and Catalyst Material (CSCM) for Sorption Enhanced Reforming (SER) of methane is presented in this paper. After hydrothermal synthesis, a nominal 30 wt% CaO-based sorbent supported on mayenite was physically mixed with a commercial reforming catalyst and granulated to obtain bifunctional particles of 200–300 μm. Materials were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller surface analysis (BET) and Mercury- intrusion prosimetry (Hg-porosimetry). A novel thermo-gravimetric analysis (TGA) approach was employed for investigating SER activity, particularly the materials performance during multicycling methane reforming and sorbent carbonation followed by regeneration in oxidative atmosphere – either in the presence of steam or CO2 at high temperature. When regeneration is carried out in 100 vol% CO2 at 925 °C, an intermediate reduction step between cycles was crucial to maintain the catalytic activity of the CSCM for 100 consecutive sorption-regeneration cycles. In spite of a stable catalytic activity, the initial sorption capacity of the CSCM sorbent function (~16gCO2/100gCSCM) declined progressively with cyclic runs and stabilized at ~10gCO2/100gCSCM from cycle 90 onwards. This decline in capacity has been related to CaO depletion by solid phase reaction with the catalyst support.

Fluidized bed reactor assisted by Oxygen Transport Membranes: Numerical simulation and experimental hydrodynamic study

In the near future, H2 is bound to become an important energy carrier used for surplus power storage and for sustainable transportation. An innovative technology for the production of a H2 rich gas is the Sorption Enhanced Reforming (SER) of hydrocarbons: a solid CaO-based sorbent is used to capture CO2 produced by reforming and water gas shift, enhancing the equilibrium. CaCO3 is decomposed in a fluidized bed oxy-combustion calciner and the sorbent recycled. In this work, the interest is focused on the Calcium Looping (CaL) cycle, more specifically on the combustor/calciner fluidized bed reactor of the pilot scale platform ZECOMIX (ENEA – 5 kmol/h of H2). The feasibility to feed O2 to a bubbling fluidized bed calciner by means of Oxygen Transport Membranes (OTM) is studied using a simulation model. The fluidizing flow rate is made of CO2 and CH4, preliminarily heated up to 700–850 °C by heat exchange with the output gas stream (above 900 °C); overall gas flow rate and methane content are enough to reach vigorous bubbling fluidization (u ≈ 10 umf) and temperature required by calcination, respectively. Cold model experimental tests with a cylindrical bubbling fluidized bed reactor with internals (vertical rods mimicking the OTM system) are carried out to support the design of the calciner unit in the ZECOMIX experimental platform. The hydrodynamic study is performed under ambient conditions to simulate fluidized bed expansion and to evaluate bubbles behavior in the calciner, in presence of vertical, tubular membranes for oxygen transfer.