Effects of supports on hydrogen production and carbon deposition of Fe-based oxygen carriers in chemical looping hydrogen generation

Chemical looping hydrogen generation (CLHG) can produce high purity hydrogen from fuel gases with inherent separation of CO₂. However, the performance of oxygen carrier in CLHG varies with the support materials. In this paper, the reactivity, carbon deposition, redox stability, hydrogen yield and purity, and sintering behavior of the Fe-based oxygen carriers were analyzed to investigate the effects of supports, i.e. Al₂O₃, SiO₂, MgAl₂O₄, ZrO₂ and YSZ (yttrium-stabilized zirconia). The results showed that the properties of the oxygen carriers, e.g. carbon deposition, reactivity and stability, mainly depended on the support and its interaction with iron oxides. The reactivity and hydrogen yield for the oxygen carriers investigated followed the order: Fe₂O₃/MgAl₂O₄ > Fe₂O₃/ZrO₂ > Fe₂O₃/YSZ > Fe₂O₃/Al₂O₃ > Fe₂O₃/SiO₂, and the order of hydrogen purity was identical with that of hydrogen yield as a result of carbon deposition. Furthermore, the hydrogen purity of the Fe-based oxygen carriers supported by MgAl₂O₄, ZrO₂, or YSZ could reach above 99.5% and Fe₂O₃/YSZ showed the lowest carbon deposition. The oxygen carriers, Fe₂O₃/MgAl₂O₄ and Fe₂O₃/SiO₂, were selected to be characterized by SEM images and XRD patterns before and after the redox cycles.     

Hydrogen production from fossil fuels with carbon capture and storage based on chemical looping systems

This paper analyzes innovative processes for producing hydrogen from fossil fuels conversion (natural gas, coal, lignite) based on chemical looping techniques, allowing intrinsic CO₂ capture. This paper evaluates in details the iron-based chemical looping system used for hydrogen production in conjunction with natural gas and syngas produced from coal and lignite gasification. The paper assesses the potential applications of natural gas and syngas chemical looping combustion systems to generate hydrogen. Investigated plant concepts with natural gas and syngas-based chemical looping method produce 500 MW hydrogen (based on lower heating value) covering ancillary power consumption with an almost total decarbonisation rate of the fossil fuels used.The paper presents in details the plant concepts and the methodology used to evaluate the performances using critical design factors like: gasifier feeding system (various fuel transport gases), heat and power integration analysis, potential ways to increase the overall energy efficiency (e.g. steam integration of chemical looping unit into the combined cycle), hydrogen and carbon dioxide quality specifications considering the use of hydrogen in transport (fuel cells) and carbon dioxide storage in geological formation or used for EOR.     

Evaluation of activated carbons based on olive stones as catalysts during hydrogen production by thermocatalytic decomposition of methane

Catalytic decomposition of methane over carbon materials has been intensively studied as an environmental approach for CO₂-free hydrogen production without further by-products except hydrogen and valuable carbon. In this work, we will investigate the catalytic activity of activated carbons based on olive stones prepared by two different processes. Additionally, the effect of three major operational parameters: temperature, weight of catalyst and flow rate of methane, was determined. Therefore, a series of experiments were conducted in a horizontal-flow fixed bed reactor. The outflow gases were analysed using a mass spectrometer. The textural, structural and surface chemistry properties of both fresh and used activated carbons were determined respectively by N₂ gas adsorption, X-Ray Diffraction and Raman and Temperature Programmed Desorption. The results reveal that methane decomposition rate increases with temperature and methane flow however it decreases with catalyst weight. The two carbon samples exhibit a high initial activity followed by a rapid decay. Textural characterization of the deactivated carbon presents a dramatic drop of surface area, pore and micropore volumes against an increase of average pore diameter confirming that methane decomposition occurs mainly in micropores. XRD characterization shows a turbostratic structure of fresh samples with more graphitization in deposed carbon explaining the lowest activity at the end of reaction. Raman spectra reveal the domination of the two bands G and D which varying intensities affirm that the different carbons tend to organise in aromatic rings. Finally the surface chemistry qualitatively changes greatly after methane dissociation for CAGOC unlike CAGOP but quantitatively a small difference is observed which indicates that these functionalities may have a role in this heterogeneous reaction but cannot be totally responsible. Among the two catalysts tested, CAGOC has the highest initial methane decomposition rate but CAGOP is the most stable one.     

Chemical looping glycerol reforming for hydrogen production by Ni@ZrO2 nanocomposite oxygen carriers

The research describes the synthesis of nanocomposite Ni@ZrO₂ oxygen carriers (OCs) and lanthanide doping effect on maintaining the platelet-structure of the nanocomposite OCs. The prepared OCs were tested in chemical looping reforming of glycerol (CLR) process and sorption enhanced chemical looping reforming of glycerol (SE-CLR) process. A series of characterization techniques including N₂ adsorption-desorption, X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution transmission electron microscopy (HRTEM), H₂ temperature-programmed reduction (H₂-TPR), H₂ pulse chemisorption and O₂ temperature-programmed desorption (O₂-TPD) were used to investigate the physical properties of the fresh and used OCs. The results show that the platelet-stack structure of nanocomposite OCs could significantly improve the metal support interaction (MSI), thus enhancing the sintering resistance. The effect of lanthanide promotion on maintaining this platelet-stack structure increased with the lanthanide radius, namely, La³⁺ > Ce³⁺ > Pr³⁺ > Yb³⁺. Additionally, the oxygen mobility was also enhanced because of the coordination of oxygen transfer channel size by doping small radius lanthanide ions. The CeNi@ZrO₂ showed a moderate ‘dead time’ of 220 s, a high H₂ selectivity of 94% and a nearly complete glycerol conversion throughout a 50-cycle CLR test. In a 50-cycle SE-CLR stability test, the CeNi@ZrO₂CaO showed high H₂ purity of 96.3%, and an average CaCO₃ decomposition percentage of 53% without external heating was achieved.     

Evaluation of iron based chemical looping for hydrogen and electricity co-production by gasification process with carbon capture and storage

Integrated Gasification Combined Cycle (IGCC) is one of power generation technologies having the highest potential for carbon capture with low penalties in efficiency and cost. Syngas produced by gasification can be decarbonised using chemical looping methods in which an oxygen carrier (usually a metallic oxide) is recycled between the syngas oxidation reactor (fuel reactor) and the chemical agent oxidation reactor (steam reactor). In this way, the resulted carbon dioxide is inherently separated from the other products of combustion and the syngas energy is transferred to an almost pure hydrogen stream suitable to be used not only for power generation but also for transport sector (PEM fuel cells).     

Microwave-assisted catalytic decomposition of methane over activated carbon for -free hydrogen production

The aim of this work was to combine microwave heating with the use of low-cost granular activated carbon as a catalyst for the production of CO₂-free hydrogen by methane decomposition in a fixed bed quartz-tube flow reactor. In order to compare the results achieved, conventional heating was also applied to the catalytic decomposition reaction of methane over the activated carbon. It was found that methane conversions were higher under microwave conditions than with conventional heating when the temperature measured was lower than or equal to . However, when the temperature was increased, the difference between the conversions under microwave and conventional heating was reduced. The influence of volumetric hourly space velocity (VHSV) on the conversion tests using both microwave and conventional heating was also studied. In general, there is a substantial initial conversion, which declines sharply during the first stages of the reaction but tends to stabilise with time. An increase in the VHSV has a negative effect on CH₄ conversion, and even more so in the case of microwave heating. Nevertheless, the conversions obtained in the microwave device at the beginning of the experiments are, in general, better than the conversions reported in other works which also use a carbonaceous-based catalyst. Additionally, the formation of carbon nanofibres in one of the microwave experiments is also reported.     

Biomass pyrolysis oils for hydrogen production using chemical looping reforming

This study considers the feasibility of using highly oxygenated and volatile pyrolysis oils from biomass wastes as sustainable liquid fuels for conversion to a hydrogen-rich syngas using the chemical looping reforming process in a packed bed. Pine oil and palm empty fruit bunches oil- ‘EFB’- were investigated with a Ni/Al₂O₃ catalyst doubling as oxygen transfer material (OTM). The effect of molar steam to carbon ratio (S/C) and weight hourly space velocity were investigated at 600 °C and atmospheric pressure on the fuel and steam conversion, the H₂ yield and the H- and C-products distribution. With a downward fuel feed configuration and using a H₂-reduced catalyst, maximum averaged fuel conversions of ∼97% for pine oil and 89% for EFB oil were achieved at S/C ratios of 2.3 and 2.6 respectively (on a water-free oil basis). This produced H₂ with a yield efficiency of approximately 60% for pine oil and 80% for EFB oil notwithstanding equilibrium limitations, and with little CH₄ by-product. Both oils exhibited very similar outputs with varying S/C. Upon a short number of cycles, i.e. starting from an oil-reduced catalyst, the fuel conversion dropped slightly but the steam conversion was constant, resulting in a slow decrease in H₂ yield. Despite their high level of oxygen content, the pyrolysis oils were shown to maintain close to 90% reduction of the oxidised catalyst upon repeated cycles, but the rate of reduction decreased with cycling.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Deep regeneration of activated carbon catalyst and autothermal analysis for chemical looping methane thermo-catalytic decomposition process

The application of a chemical looping process to methane thermo-catalytic decomposition using activated carbon (AC) as a catalyst has been recognized as a promising technology for continuous high-purity H₂ production in a carbon constrained world. However, it usually needs an external heat supply for the endothermic decomposition reactions. By taking advantage of the chemical looping combustion (CLC) technology, this study proposed a deep regeneration approach using H₂O and O₂ as regeneration agents to overcome the issues with maintaining catalytic activity and producing the heat needed for the endothermic reactions of H₂ production from methane. TG-DTA and bench scale fluidized bed experimental results indicate that a deep regeneration degree of 30% or above could completely reactivate the spent AC catalyst and simultaneously generate sufficient heat than required in the methane decomposition reaction. Characterization study implies that the deep regenerated AC catalyst could maintain its physical properties within a certain number of cycles. Based on the experimental results, the chemical looping methane thermo-catalytic decomposition process was further optimized and assessed by Aspen Plus^® thermodynamic simulation. The results indicate that heat and mass balances could be attained, and the circulation of the AC catalyst with a temperature difference of 262 °C between the decomposer and the regenerator enabling the process to run autothermally.     

Evaluation of syngas-based chemical looping applications for hydrogen and power co-generation with CCS

This paper evaluates hydrogen and power co-generation based on coal-gasification fitted with an iron-based chemical looping system for carbon capture and storage (CCS). The paper assess in details the whole hydrogen and power co-production chain based on coal gasification. Investigated plant concepts of syngas-based chemical looping generate about 350–450 MW net electricity with a flexible output of 0–200 MW_th hydrogen (based on lower heating value) with an almost total decarbonisation rate of the coal used.     

An energy-efficient plasma methane pyrolysis process for high yields of carbon black and hydrogen

A novel thermal plasma process was developed, which enables economically viable commercial-scale hydrogen and carbon black production. Key aspects of this process are detailed in this work. Selectivity and yield of both solid, high-value carbon and gaseous hydrogen are given particular attention. For the first time, technical viability is demonstrated through lab scale reactor data which indicate methane feedstock conversions of >99%, hydrogen selectivity of >95%, solid recovery of >90%, and the ability to produce carbon particles of varying crystallinity having the potential to replace traditional furnace carbon black. The energy intensity of this process was established based on real-time operation data from the first commercial plant utilizing this process. In its current stage, this technology uses around 25 kWh per kg of H2 produced, much less than water electrolysis which requires approximately 60 kWh per kg of H2 produced. This energy intensity is expected to be reduced to 18–20 kWh per kg of hydrogen with improved heat recovery and energy optimization.     

Thermodynamic investigation on hydrogen production via self-sufficient chemical looping reforming of glycerol (CLRG) using metal oxide oxygen carriers

The self-sufficient chemical looping reforming of glycerol (CLRG) utilizes the same basic principles as chemical looping combustion (CLC), the main difference being that the desired product in CLRG is not heat but H₂. Therefore, in the CLR process the O/C ratio is kept low to prevent the complete oxidation of glycerol to H₂O. A systematic thermodynamic study of CLRG using metal oxide oxygen carriers (NiO, CuO, CoO, Co₃O₄, Mn₃O₄, Mn₂O₃ and Fe₂O₃) is performed to analyze the product yield, carbon deposition and energy requirements at different temperatures and pressures. The calculation results show higher temperatures promote, but higher pressures inhibit H₂ production. Favorable conditions (800 °C and 1 atm) are obtained for H₂ manufacture from CLRG process. CuO is the best performing oxygen carrier followed by Mn-based oxygen carriers, while Fe₂O₃ is the least preferred oxygen carrier for CLRG. These results obtained in this theoretical study can offer helpful information for CLRG experimental tests.     

Chemical looping gasification for hydrogen production: A comparison of two unique processes simulated using ASPEN Plus

The research compares the simulations of two chemical looping gasification (CLG) types using the ASPEN Plus simulation software for the production of H₂. The simulated biomass type was poultry litter (PL). The first CLG type used in situ CO₂ capture utilizing a CaO sorbent, coupled with steam utilization for tar reforming, allowing for the production of a CO₂-rich stream for sequestration. Near-total sorbent recovery and recycle was achieved via the CO₂ desorption process. The second type utilized iron-based oxygen carriers in reduction–oxidation cycles to achieve 99.8% Fe₃O₄ carrier recovery and higher syngas yields. Temperature and pressure sensitivity analyses were conducted on the main reactors to determine optimal operating conditions. The optimal temperatures ranged from 500 to 1250 °C depending on the simulation and reactor type. Atmospheric pressure proved optimal in all cases except for the reducer and oxidizer in the iron-based CLG type, which operated at high pressure. This CLG simulation generated the most syngas in absolute terms (2.54 versus 0.79 kmol/kmol PL), while the CO₂ capture simulation generated much more H₂-rich syngas (92.45 mol-% compared to 62.94 mol-% H₂).     

Modeling chemical looping syngas production in a microreactor using perovskite oxygen carriers

Synthesis gas, a mixture of hydrogen and carbon monoxide, could be produced in a chemical looping process. The objective of this work is the modeling of syngas production in a fixed bed microreactor by chemical looping reforming. A perovskite oxygen carrier was used for the reduction of methane to syngas. Twenty one gas-solid kinetic models were applied to the experimental data in which their parameters were estimated using an optimization code. The results show that among all models, reaction order model is the most preferable choice with satisfactory fitting criteria. The gas-solid model was coupled with a catalytic scheme to predict not only the conversion of perovskite oxygen carrier, but also the catalytic performance of the solid particles for syngas production. The kinetic parameters of the unified model were evaluated based on the experimental data of a fixed bed reactor. Analysis of both perovskite and nickel oxide, oxygen carriers shows that perovskite particles could convert 50 times slower than those of nickel oxide. A H₂/CO ratio of below 10 was obtained in a period of time. A large amount of hydrogen was produced after completing gas-solid reactions which was due to cracking of methane to carbon and hydrogen. Although hydrogen was the main outlet product afterwards, corresponding carbon formation is a problem which should be avoided. The reduction of methane was proposed before 500 s with a carbon formation of below 0.04 kg carbon per one kg of perovskite carrier. Solid reduction conversion, methane consumption and product distribution were analyzed inside the microreactor.     

Diameter-controlled carbon nanotubes and hydrogen production

Simultaneous production of hydrogen and carbon nanomaterials over Ni-loaded ZSM-5 catalysts via catalytic decomposition of methane was investigated. The effects of nickel particle size and reaction temperature on the hydrogen production, catalyst deactivation and the morphologies of the carbon nanotubes were investigated. Two catalyst were prepared: Ni/ZSM-5(300) – predominant size of the Ni particles 30–60 nm and nNi/ZSM-5(300) predominant size of the Ni particles 10–20 nm.     

Effects of reaction conditions on hydrogen production and carbon nanofiber properties generated by methane decomposition in a fixed bed reactor using a NiCuAl catalyst

In this paper, the results obtained in the catalytic decomposition of methane in a fixed bed reactor using a NiCuAl catalyst prepared by the fusion method are presented. The influences of reaction temperature and space velocity on hydrogen concentration in the outlet gases, as well as on the properties of the carbon produced, have been investigated. Reaction temperature and the space velocity both increase the reaction rate of methane decomposition, but also cause an increase in the rate of catalyst deactivation. Under the operating conditions used, the carbon product is mainly deposited as nanofibers with textural properties highly correlated with the degree of crystallinity.     

Hydrogen and electricity co-production plant integrating steam-iron process and chemical looping combustion

In this paper, steam-iron process (Fe looping) and NiO-based chemical looping combustion (Ni looping) are integrated for hydrogen production with inherent separation of CO₂. An integrated combined cycle based on the Fe and Ni loopings is proposed and modeled using Aspen Plus software. The simulation results show that at Fe-SR 815 °C, Fe-FR 815 °C, Ni-FR 900 °C and Ni-AR 1050 °C without supplementary firing, the co-production plant has a net power efficiency 14.12%, hydrogen efficiency 33.61% and an equivalent efficiency 57.95% without CO₂ emission. At a supplementary firing temperature of 1350 °C, the net power efficiency, hydrogen efficiency and the equivalent efficiency are 27.47%, 23.39% and 70.75%, respectively; the CO₂ emission is 365.36 g/kWh. The plant is attractive because of high-energy conversion efficiency and relatively low CO₂ emission; moreover, the hydrogen/electricity ratio can be varied in response to demand. The influences of iron oxide recycle rate, supplementary firing temperature, inert support addition and other parameters on the system performance are also investigated in the sensitive analyses.     

Study of the deactivation mechanism of carbon blacks used in methane decomposition

Carbon blacks have recently gained attention as suitable catalysts for the CO_x-free hydrogen production by thermo-catalytic decomposition of methane (TCD) because of their stability and efficiency. In the present work, several commercial carbon blacks were studied as catalysts for the TCD of methane by varying the temperature and the methane space velocity. The BP2000 carbon black sample, which showed the highest activity in methane decomposition per mass of catalyst, was studied more thoroughly. Despite BP2000 exhibiting stable activity in the TCD of methane during several hours on stream, a long duration run carried out at 950 °C revealed that it finally became deactivated. The changes in the physicochemical properties (textural properties, surface chemistry and crystallinity) of the BP2000 sample at different stages of the catalyst lifetime were measured, and the main results obtained are presented here. The paper also discusses the potential of the production of a wide range of hydrogen–methane mixtures, which can be directly fed to an internal combustion engine, by means of TCD with carbonaceous catalysts.     

High temperature iron-based catalysts for hydrogen and nanostructured carbon production by methane decomposition

The production of hydrogen and filamentous carbon by means of methane decomposition was investigated in a fixed-bed reactor using iron-based catalysts. The effect of the textural promoter and the addition of Mo as a dopant affects the catalysts performance substantially: iron catalyst prepared with Al₂O₃ showed slightly higher catalytic performance as compared to those prepared with MgO; Mo addition was found to improve the catalytic performance of the catalyst prepared with MgO, whereas in the catalyst prepared with Al₂O₃ displayed similar or slightly poorer results. Additionally, the influence of the catalyst reduction temperature, the reaction temperature and the space velocity on the hydrogen yield was thoroughly investigated. The study reveals that iron catalysts allow achieving high methane conversions at operating temperatures higher than 800 °C, yielding simultaneously carbon nanofilaments with interesting properties. Thus, at 900 °C reaction temperature and 1 l g⁻¹_cat h⁻¹ space velocity, ca. 93 vol% hydrogen concentration was obtained, which corresponds to a methane conversion of 87%. Additionally, it was found that at temperatures higher than 700 °C, carbon co-product is deposited mainly as multi walled carbon nanotubes. The textural and structural properties of the carbonaceous structures obtained are also presented.     

Novel quasi-autothermal hydrogen production process in a fixed-bed using a chemical looping approach: A numerical study

This paper presents a novel quasi-autothermal hydrogen production process. The proposed layout couples a Chemical Looping Combustion (CLC) section and a Steam Methane Reforming (SMR) one. In CLC section, four packed-beds are operated using Ni as oxygen carrier and CH₄ as fuel to continuously produce a hot gaseous mixture of H₂O and CO₂. In SMR section, two fixed-beds filled with Ni-based catalyst convert CH₄ and H₂O into a H₂-rich syngas. Four heat exchangers were employed to recover residual heat content of all the exhaust gas currents. By means of a previously developed 1D numerical model, a dynamic simulation study was carried out to evaluate feasibility of the proposed system in terms of methane conversion (100% circa), hydrogen yield (about 0.65 mol_H2/mol_CH4) and selectivity (about 70%), and syngas ratio (about 2.3 mol_H2/mol_CO). Energetic and environmental analyses of the system performed with respect to conventional steam methane reforming, highlights an energy saving of about 98% and avoided CO₂ emission of about 99%.