Semi-continuous hydrogen production from catalytic methane decomposition using a fluidized-bed reactor

Non-oxidative, catalytic decomposition of hydrocarbons is an alternative, one-step process to produce pure hydrogen with no production of carbon oxides or higher hydrocarbons. Carbon produced from the decomposition reaction, in the form of potentially valuable carbon nanotubes, remains anchored to the active catalyst sites in a fixed bed. To facilitate periodical removal of this carbon from the reactor and to make hydrogen production continuous, a fluidized-bed reactor was envisioned. The hypothesis that the tumbling and inter-particle collisions of bed material would efficiently separate nanotubes anchored to the active catalyst sites of the bed particles was tested and shown to be invalid. However, a switching mode reaction system for the semi-continuous production of hydrogen and carbon nanotubes by periodic removal and replenishment of the catalytic bed material has been successfully demonstrated.     

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.     

Effect of hydrogen additive on methane decomposition to hydrogen and carbon over activated carbon catalyst

The effect of H₂ addition on CH₄ decomposition over activated carbon (AC) catalyst was investigated. The results show that the addition of H₂ to CH₄ changes both methane conversion over AC and the properties of carbon deposits produced from methane decomposition. The initial methane conversion declines from 6.6% to 3.3% with the increasing H₂ flowrate from 0 to 25 mL/min, while the methane conversion in steady stage increases first and then decreases with the flowrate of H₂, and when the H₂ flowrate is 10 mL/min, i.e. quarter flowrate of methane, the methane conversion over AC in steady stage is four times more than that without hydrogen addition. It seems that the activity and stability of catalyst are improved by the introduction of H₂ to CH₄ and the catalyst deactivation is restrained. Filamentous carbon is obtained when H₂ is introduced into CH₄ reaction gas compared with the agglomerate carbon without H₂ addition. The formation of filamentous carbon on the surface of AC and slower decrease rate of surface area and pores volume may cause the stable activity of AC during methane decomposition.     

Hierarchical porous carbon catalyst for simultaneous preparation of hydrogen and fibrous carbon by catalytic methane decomposition

Direct coal liquefaction residue was used as the precursor for preparing hierarchical micro-/macro-mesoporous carbon by KOH activation with addition of Al₂O₃, and the resultant carbon AlRC was used as the catalyst for catalytic methane decomposition. The results indicate that the carbon AlRC shows excellent methane conversion, up to 61% after 10 h. Besides hydrogen production from methane decomposition, fibrous carbons were formed on the AlRC catalyst, which is different from other carbon catalysts. The investigations of the formation and growth of the fibrous carbon on the carbon catalyst and its catalytic performance indicated that the formed fibrous carbon contribute to the high methane conversion of AlRC catalyst.     

One-dimensional model of solar thermal reactors for the co-production of hydrogen and carbon black from methane decomposition

The solar thermal decomposition of methane is a promising route for the large scale production of hydrogen and carbon black with zero CO₂ emissions, however careful control of the reactor is required to ensure product particles of specific sizes. A one-dimensional model employing a sectional method is developed to simulate the evolution of polydisperse fresh and seed particle populations in an indirectly heated solar reactor. The model accounts for the homogeneous nucleation of fresh particles, the heterogeneous growth of the fresh and seed particles, particle coagulation, and the growth of carbon on the walls of the reactor from heterogeneous reaction and particle deposition. The heat transport mechanisms modelled include wall-gas convection, wall-particle radiation exchange, particle-gas convection and heat release from chemical reaction. The model is validated in terms of methane conversion against a 10 kW experimental solar reactor and used to extract kinetic parameters for the homogeneous and heterogeneous reaction paths. The model shows promise as a quick and simple tool for the design and control of industrial scale solar reactors.     

Production of COx-free hydrogen by the thermal decomposition of methane over activated carbon: Catalyst deactivation

Hydrogen, an environment-friendly energy source, is deemed to become strongly in demand over the next decades. In this work, CO_x-free hydrogen was produced by the thermal catalytic decomposition (TCD) of methane by a carbon catalyst. Deactivated catalysts at four-stage of progressive were characterized by nitrogen sorption and scanning electron microscopy. TCD of methane at 820 and 940 °C was about 13- and 8-folds higher than non-catalytic decomposition, respectively. High temperatures positively affected the kinetics of hydrogen production but negatively influenced the total amount of hydrogen and carbon products. The total pore volume was a good indicator of the total amount of hydrogen product. Catalyst activity was decreased because of the changes in the catalyst's textural properties within three ranges of relative time, that is, 0 to 45, 0.45 to 0.65, and 0.65 to 1. Models for specific surface area and total pore volume as functions of catalyst deactivation kinetics were developed.     

Co-production of hydrogen and carbon black from solar thermal methane splitting in a tubular reactor prototype

This study addresses the solar thermal decomposition of natural gas for the co-production of hydrogen and carbon black (CB) as a high-value nano-material with the bonus of zero CO₂ emission. The work focused on the development of a medium-scale solar reactor (10 kW) based on the indirect heating concept. The solar reactor is composed of a cubic cavity receiver (20 cm-side), which absorbs concentrated solar irradiation through a quartz window by a 9 cm-diameter aperture. The reacting gas flows inside four graphite tubular reaction zones that are settled vertically inside the cavity. Experimental results in the temperature range 1740-2070 K are presented: acetylene (C₂H₂) was the most important by-product with a mole fraction of up to about 7%, depending on the gas residence time. C₂H₂ content in the off-gas affects drastically the carbon yield of the process. The effects of temperature and residence time are analyzed. A preliminary process study concerning a 55 MW solar chemical plant is proposed on the basis of a process flow sheet. Results show that 1.7 t/h of hydrogen and 5 t/h of CB could be produced with an hydrogen cost competitive to conventional steam methane reforming.     

Hydrogen production from thermo-catalytic decomposition of methane using carbon black catalysts in an indirectly-irradiated tubular packed-bed solar reactor

The solar thermo-catalytic decomposition of methane using carbon black catalysts for CO₂-free hydrogen production is studied in a packed-bed reactor. The indirectly-irradiated reactor is based on a cavity receiver and a tube-type absorber in which a given load of particle catalyst is injected during on-sun operation, while enabling multiple refilling for catalyst replacement. Concentrated solar power is used as an external radiative source for supplying the high temperature process heat and for driving the endothermic reaction. The indirect irradiation via the intermediate opaque tubular absorber results in a more uniform heating of the whole reacting bed volume and thus an easier reaction temperature control and determination. Carbon particles are used for enhancing the rate of the heterogeneous decomposition reaction and the coupling of the reactor with a particle injection system is implemented to operate in semi-continuous mode with possibility of catalyst load renewal after deactivation.     

Thermocatalytic decomposition of methane for hydrogen production using activated carbon catalyst: Regeneration and characterization studies

A series of experiments was conducted to study the deactivation and regeneration of activated carbon catalyst used for methane thermocatalytic decomposition to produce hydrogen. The catalyst becomes deactivated due to carbon deposition and six decomposition cycles of methane at temperatures of 850 and 950 °C, and five cycles of regeneration by using CO₂ at temperatures of 900, 950 and 1000 °C were carried out to evaluate the stability of the catalyst. The experiment was conducted by using a thermobalance by monitoring the mass gain during decomposition or the mass lost during the regeneration with time. The initial activity and the ultimate mass gain of the catalyst decreased after each regeneration cycle at both reaction temperatures of 850 and 950 °C, but the amount is smaller under the more severe regenerating conditions. For the reaction at 950 °C, comparison between the first and sixth reaction cycles shows that the initial activity decreased by 69, 51 and 42%, while the ultimate mass gain decreased by 62%, 36% and 16% when CO₂ gasification carried out at 900, 950 and 1000 °C respectively. Temperature -programmed oxidation profiles for the deactivated catalyst at reaction temperature of 950 °C and after several cycles showed two peaks which are attributed to different carbon characteristics, while one peak was obtained when the experiment was carried out at 850 °C. In conclusion, conducting methane decomposition at 950 °C and regeneration at 1000 °C showed the lowest decrease in the mass gain with reaction cycles.     

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.     

Unsupported nickel catalyst prepared from nickel foam for methane decomposition and recycling the carbon deposited spent catalyst

Catalytic methane decomposition (CMD) receives increasing attention for co-production of CO_x-free hydrogen and valuable carbon by-product, and the catalyst plays a crucial role on methane conversion and the product features. Unsupported nickel catalysts derived from commercial nickel foam (NF) were prepared for CMD by mild pre-treatment. Effects of the pre-treatment method (acid treatment, thermal treatment, acid-thermal treatment and hydrogen reduction) and reaction temperature were explored on the NF morphology and CMD reactivity in a fixed-bed reactor. It is found that catalytic performance of the NF-based catalyst is highly dependent on the pre-treatment and reaction temperature. The thermal and acid-thermal treatments could greatly promote the catalytic activity (with methane conversion up to 74.6% and 91.8%, respectively) at 850 °C. To fully release potential abilities of the catalyst, the carbon deposited spent catalyst was recycled as a fresh catalyst in the CMD test by several strategies. High and stable methane conversion (up to around 90%–93%) can be achieved by simulating the operation model in a fluidized-bed reactor for a continuous CMD process. Besides, the carbon deposited spent catalyst could serve as a promising candidate of supercapacitor electrode material.     

Effect of coexistence of siloxane on production of hydrogen and nanocarbon by methane decomposition using Fe catalyst

Biogas derived from sewage sludge contains CO₂, siloxane, and methane. In this study, the effect of coexistence of siloxane on the production of hydrogen and carbon nanofiber by methane decomposition using iron oxide-alumina catalyst was investigated. The catalyst was reduced by heating in a flow of methane. Siloxane addition to methane caused a catalytic activity at lower temperatures, shortened the induction period prior to the activity, and accelerated catalytic deactivation. Thermal decomposition of siloxane can occur at a lower temperature compared to that of methane. Carbon species formed by the siloxane decomposition may have a higher reducibility than methane does. The reactivity may lead to a carbon deposition at a lower temperature. Coexistence of CO₂ and siloxane can prolong a catalytic lifetime because CO₂ may inhibit the carbon deposition on catalyst to some extent.     

Experimental and numerical analysis of a methane thermal decomposition reactor

An indirectly heated tubular reactor is fabricated and used to study methane thermal decomposition conversion and determine kinetic parameters. A combined perfectly mixed reactor with bypass (CPMR) is proposed as an alternative to the traditional perfectly mixed and plug flow reactors. The CPMR model is used in order to account for buoyancy flow in the reactor. Results comparing the numerical predictions from all three models to experimental data show that buoyancy effects are significant in the reactor under study and also in most reactors in the literature. Including this effect might significantly improve the accuracy of the model predictions. The CPMR reactor model with a reaction rate constant of 5.43 × 10¹⁵ 1/s and an activation energy of 420.7 kJ/mol is capable of reproducing the obtained experimental data in this study and in the literature.     

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.     

A pilot-scale solar reactor for the production of hydrogen and carbon black from methane splitting

A pilot-scale solar reactor was designed and operated at the 1 MW solar furnace of CNRS for H₂ and carbon black production from methane splitting. This constitutes the final objective of the SOLHYCARB EC project. The reaction of CH₄ dissociation produces H₂ and carbon nanoparticles without CO₂ emissions and with a solar upgrade of 8% of the high heating value of the products. The reactor was composed of 7 tubular reaction zones and of a graphite cavity-type solar receiver behaving as a black-body cavity. Temperature measurements around the cavity showed a homogeneous temperature distribution. The influence of temperature (1608K–1928K) and residence time (37–71 ms) on methane conversion, hydrogen yield, and carbon yield was especially stressed. For 900 g/h of CH₄ injected (50% molar, the rest being argon) at 1800K, this reactor produced 200 g/h H₂ (88% H₂ yield), 330 g/h CB (49% C yield) and 340 g/h C₂H₂ with a thermal efficiency of 15%. C₂H₂ was the most important by-product and its amount decreased by increasing the residence time. A 2D thermal model of the reactor was developed. It showed that the design of the reactor front face could be drastically improved to lower thermal losses. The optimised design could reach 77% of the ideal black-body absorption efficiency (86% at 1800K), i.e. 66%.     

Parametric study of the decomposition of methane using a NiCu/Al2O3 catalyst in a fluidized bed reactor

CO₂-free production of hydrogen via catalytic decomposition of methane (CDM) was studied in a fluidized bed reactor (FBR) using a NiCu/Al₂O₃ catalyst. A parametric study of the effects of some process variables, including catalyst particle size, reaction temperature, space velocity and the ratio of gas flow velocity to the minimum fluidization velocity (u_o/u_mf), was undertaken. A mean particle size of 150 μm allows optimization of results in terms of hydrogen production without agglomeration problems. The operating conditions strongly affect the catalyst performance: hydrogen production was enhanced by increasing operating temperature and lowering space velocity. However, increases in operating temperature, space velocity and the ratio u_o/u_mf provoked increases in the catalyst deactivation rate. At 700 °C, carbon was deposited as carbon nanofibers, while higher temperatures promoted the formation of encapsulating carbon, which led to rapid catalyst deactivation.     

Life cycle assessment of hydrogen production by methane decomposition using carbonaceous catalysts

Methane decomposition to yield hydrogen and carbon (CH₄ ? 2H₂ + C) is one of the cleanest alternatives, free of CO₂ emissions, for producing hydrogen from fossil fuels. This reaction can be catalyzed by metals, although they suffer a fast deactivation process, or by carbonaceous materials, which present the advantage of producing the catalyst from the carbon obtained in the reaction. In this work, the environmental performance of methane decomposition catalyzed by carbonaceous catalysts has been evaluated through Life Cycle Assessment tools, comparing it to other decomposition processes and steam methane reforming coupled to carbon capture systems. The results obtained showed that the decomposition using the autogenerated carbonaceous as catalyst is the best option when reaction conversions higher than 65% are attained. These were confirmed by 2015 and 2030 forecastings. Moreover, its environmental performance is highly increased when the produced carbon is used in other commercial applications. Thus, for a methane conversion of 70%, the application of 50% of the produced carbon would lead to a virtually zero-emissions process.     

Deactivation of palm shell-based activated carbon catalyst used for hydrogen production by thermocatalytic decomposition of methane

Thermocatalytic decomposition of methane over activated carbon acting as a catalyst is proposed as a potential alternative for hydrogen production. However, over a certain duration catalyst becomes deactivated due to intensive carbon deposition.