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.     

H2 production from methane pyrolysis over commercial carbon catalysts: Kinetic and deactivation study

Hydrogen production from catalytic methane decomposition (DeCH₄) is a simple process to produce high purity hydrogen with no formation of carbon oxides (CO or CO₂). However, to completely avoid those emissions, the catalyst must not be regenerated. Therefore, it is necessary to use inexpensive catalysts, which show low deactivation during the process. Use of carbon materials as catalysts fulfils these requirements.     

Coal char gasification for co-production of fuel gas and methane decomposition catalysts

Partial gasification of coal char was conducted with addition of metal oxides for co-production of fuel gas and methane decomposition catalysts. Effect of the metal composition (Ni, Co and Fe based mono- or bi-metals) was investigated on the fuel gas production and the resultant catalyst surface and textural properties, morphology and performance in catalytic methane decomposition (CMD). Besides H₂-rich fuel gas production (the combustion energy up to 11.03–23.42 MJ/kg_char) from the gasification, the gasification residue can directly serve as the effective and efficient catalyst for CMD. The Fe and Fe–Co composite oxides were found to be better among the mono- and bi-metallic oxides for the fuel gas production during the gasification, respectively. The Ni-based mono-/bi-metallic catalysts could display high and stable methane conversion (up to 80%) during the 600-min CMD test at 850 °C. Promotional role of the second metal in CMD was discussed on the carbon diffusion, metal mobility and reducibility, formation and growth of the deposited carbons. The formed carbon morphology after CMD was analyzed based on the Kirkendall effect and Tammann temperature and further correlated to the potential catalyst deactivation.     

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.     

Hydrogen via methane decomposition: an application for decarbonization of fossil fuels

Fossil fuel decarbonization is an emerging technological approach for significant reduction of CO₂ emissions into the atmosphere. CO₂-free production of hydrogen via thermocatalytic decomposition of methane (natural gas) as a viable decarbonization strategy is discussed in this paper. The technical approach is based on a single-step decomposition (pyrolysis) of methane and other hydrocarbons over carbon-based catalysts in an air/water free environment. This approach eliminates the need for water–gas shift and CO₂ removal stages, required by conventional processes (e.g. methane steam reforming), which significantly simplifies the process. Clean carbon is produced as a valuable byproduct of the process. The experimental data on the catalytic activity of different carbon-based catalysts in methane decomposition reaction are presented in this work. The paper also discusses various conceptual designs for the reactor suitable for decomposition of methane with production of hydrogen-rich gas and continuous withdrawal of elemental carbon.     

Ni doped carbons for hydrogen production by catalytic methane decomposition

Ni doped carbons were prepared from raw coal and direct coal liquefaction residue (CLR) by KOH activation with addition of Ni(NO₃)₂, and used for catalytic methane decomposition (CMD) to produce hydrogen. The catalytic activity of the Ni doped carbon for CMD was compared with those of metal catalysts (Ni/SiO₂ and Ni/Al₂O₃), coal- and CLR-based carbons, and Ni-carbon catalysts prepared by traditional impregnation and precipitation methods. The results show that the Ni doped carbon has higher and more stable activity than the metal and carbon catalysts at 850 °C. The preparation method for Ni doped carbons can make full use of the reducibility of the carbon composition and simplify the traditional synthesis process. The Ni content and the morphology of carbon deposits produced during CMD have a great effect on the catalytic activity of the Ni doped carbon.     

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.     

Use of a swirling flow to mechanically regenerate catalysts after methane decomposition

A new device is proposed to regenerate catalysts after hydrogen production via methane decomposition. Because carbon deposition inhibits catalytic reactions, carbon removal is indispensable for continuous hydrogen production. This device generated a swirling flow by gas supplied at the top and bottom along the inner surface of a tube. The swirling flow rotated the catalyst particles in the tube. Shear stresses on the particles caused by inter-particle and particle-wall impacts led to attrition. Carbon was mechanically removed from the particles by attrition and was elutriated with the flue gas. Ten cycles of methane decomposition and catalyst regeneration were performed using reduced ilmenite as a catalyst. Carbon was clearly removed by catalyst regeneration. Stable regeneration was confirmed by examination of weight changes of the particles caused by carbon deposition and removal during the cycles. Hydrogen production increased by 10% during the cycles than during continuous methane decomposition for 4 h.     

Methane decomposition to pure hydrogen and carbon nano materials: State-of-the-art and future perspectives

Hydrogen is a clean fuel widely used in fuel cells, engines, rockets and many other devices. The catalytic decomposition of methane (CDM) is a CO_x-free hydrogen production technology from which carbon nano materials (CNMs) can be generated as a high value-added byproduct for electrode, membranes and sensors. Recent work has focused on developing a low cost catalyst that could work without rapid deactivation by carbon deposition. In this review, the economic and environmental evaluation of CDM are compared with coal gasification, steam reforming of methane, and methanol steam reforming in terms of productivity, CO₂ emissions, and H₂ production and cost. CDM could be a favorable technology for on-site demand-driven hydrogen production on a small or medium industrial scale. This study covers the Fe-based, Ni-based, noble metal, and carbonaceous catalysts for the CDM process. Focusing on hydrogen (or carbon) yield and production cost, Fe-based catalysts are preferable for CDM. Although Ni-based catalysts showed a much higher hydrogen yield with 0.39 mol_H2/g_cat./h than Fe-based catalysts with 0.22 mol_H2/g_cat./h, the hydrogen cost of the former was estimated to be 100-fold higher ($0.89/$0.009). Further, the CDM performance on different types of reactors are detailed, whereas the molten-metal catalyst/reactor is suggested to be a promising route to commercialize CDM. Finally, the formation mechanism, characterization, and utilization of carbon byproducts with different morphologies and structures are described and analyzed. Versus other reviews, this review shows that cheap Fe-based catalysts (10 tons H₂/1 ton iron ore) and novel molten-metal reactors (95% methane conversion) for CDM are feasible research directions for a fundamental understanding of CDM. The CNMs by CDM could be applied to the waste water purification, lubricating oils, and supercapacitors.     

Literature review of the catalytic pyrolysis of methane for hydrogen and carbon production

This review highlights recent developments and future perspectives in CO_x-free hydrogen production through methane pyrolysis. We give detailed discussions on thermal and catalytic methane cracking into hydrogen and carbon. Various types of solid and liquid catalysts were reviewed in terms of hydrogen selectivity, methane conversion, and deactivation. Some pilot scale technology was discussed; however, large-scale industrialisation is impeded by rapid solid catalyst deactivation, low-priced carbon (by-product) of molten catalysts, harsh conditions for reactor materials, and performance of stable molten catalysts. For catalytic methane cracking in molten catalysts (salt or metal), substantial advances in catalyst development, product separation, and reactor design are still required to commercialise methane pyrolysis for hydrogen production. To provide guidance to future works in this area, the review is specifically focused on (i) design of catalysts (ii) recent developments of molten salt-based methane cracking, (iii) reactor design and process design.     

In situ generation of nickel/carbon catalysts by partial gasification of coal char and application for methane decomposition

Catalytic methane decomposition (CMD) has a good potential to develop environmentally friendly hydrogen economy, and the catalyst plays a vital role on its applications. In this work, a novel strategy was proposed to fabricate efficient and effective nickel/carbon catalysts for CMD by introducing some additional nickel and K₂CO₃ into partial steam gasification of coal char. The gasification process is conducive to in situ synthesize nickel crystallites with high reduction degree (the value of Ni⁰/(Ni⁰+Ni²⁺) up to 76%–81%) on the catalyst surface, and it is competent for co-generation of hydrogen-rich gas and nickel/carbon hybrids with large surface areas (around 86–149 m²/g after washing off the residual potassium salts). The nickel/carbon hybrid as the gasification residue could serve as the catalyst for CMD, showing high and stable methane conversion (up to 80%–87%) at 850 °C. It is observed that co-production of hydrogen and filamentous carbons can be achieved in the 600-min process of CMD, thanks to the positive effect of K₂CO₃ on formation and activity improvement of the nickel/carbon catalyst.     

Methane catalytic decomposition over ordered mesoporous carbons: A promising route for hydrogen production

Methane decomposition offers an interesting route for the CO₂-free hydrogen production. The use of carbon catalysts, in addition to lowering the reaction temperature, presents a number of advantages, such as low cost, possibility of operating under autocatalytic conditions and feasibility of using the produced carbons in non-energy applications. In this work, a novel class of carbonaceous materials, having an ordered mesoporous structure (CMK-3 and CMK-5), has been checked as catalysts for methane decomposition, the results obtained being compared to those corresponding to a carbon black sample (CB-bp) and two activated carbons, presenting micro- (AC-mic) and mesoporosity (AC-mes), respectively. Ordered mesoporous carbons, and especially CMK-5, possess a remarkable activity and stability for the hydrogen production through that reaction. Under both temperature programmed and isothermal experiments, CMK-5 has shown to be a superior catalyst for methane decomposition than the AC-mic and CB-bp materials. Likewise, the catalytic activity of CMK-5 is superior to that of AC-mes in spite of the presence of mesoporosity and a high surface area in the latter. The remarkable stability of the CMK-5 catalyst is demonstrated by the high amount of carbon deposits that can be formed on this sample. This result has been assigned to the growth of the carbon deposits from methane decomposition towards the outer part of the catalyst particles, avoiding the blockage of the uniform mesopores present in CMK-5. Thus, up to 25 g of carbon deposits have been formed per gram of CMK-5, while the latter still retains a significant catalytic activity.     

Metallic and carbonaceous –based catalysts performance in the solar catalytic decomposition of methane for hydrogen and carbon production

Solar catalytic decomposition of methane (SCDM) was investigated in a solar furnace facility with different catalysts. The aim of this exploratory study was to investigate the potential of the catalytic methane decomposition approach providing the reaction heat via solar energy at different experimental conditions. All experiments conducted pointed out to the simultaneous production of a gas phase composed only by hydrogen and un-reacted methane with a solid product deposited into the catalyst particles varying upon the catalysts used: nanostructured carbons either in form of carbon nanofibers (CNF) or multi-walled carbon nanotubes (MWCNT) were obtained with the metallic catalyst whereas amorphous carbon was produced using a carbonaceous catalyst. The use of catalysts in the solar assisted methane decomposition present some advantages as compared to the high temperature non-catalytic solar methane decomposition route, mainly derived from the use of lower temperatures (600–950 °C): SCDM yields higher reaction rates, provides an enhancement in process efficiency, avoids the formation of other hydrocarbons (100% selectivity to H₂) and increases the quality of the carbonaceous product obtained, when compared to the non-catalytic route.     

A perspective on the production of hydrogen from solar-driven thermal decomposition of methane

In addition to “green” hydrogen from electrolysis of the water molecule with solar-photovoltaic or wind electricity, and “white” hydrogen, based on solar-thermal driven thermochemical splitting of the water molecule, there is another emerging opportunity to produce CO2 free hydrogen at a reduced cost. The perspective advocates in favor of “aquamarine” hydrogen, based on the solar-thermal driven thermal decomposition of methane. This pathway has an energy requirement that is much less than white and green hydrogen, and even if based on hydrocarbon fuel, has no direct production of CO₂ as a by-product, but rather carbon particles of commercial interest. Catalytic methane decomposition can be based on self-standing/supported metal-based catalysts such as Fe, Ni, Co, and Cu, metal oxide supports such as SiO₂, Al₂O₃, and TiO₂, and carbon-based catalysts such as carbon blacks, carbon nanotubes, and activated carbons, the pathway of higher technology readiness level (TRL). Thus, catalytic methane decomposition appears to be a highly promising approach, with undoubtedly many challenges, but also huge opportunities following pathways to be further refined through research and development (R&D).     

Effect of coexistence of H2S on production of hydrogen and solid carbon by methane decomposition using Fe catalyst

Biogas derived from livestock manure and food residue contains CO₂ and H₂S as well as methane. The effect of CO₂ and H₂S coexistence on the production of hydrogen and solid carbon by methane decomposition over iron oxide catalysts was investigated. The catalytic activity for methane decomposition was decreased by the coexistence of H₂S. Moreover, the activity decrease was aggravated by the coexistence of CO₂ as well as H₂S, and higher temperature was required to mitigate the activity decrease by the coexistence of CO₂. By increasing the amount of catalyst, the upstream catalyst was preferentially poisoned, but the downstream catalyst developed catalytic activity thanks to its sacrifice. With 2 g of catalyst, the maximum conversion of pure methane was about 85% at 840 °C, but it was slightly less than 80% in the presence of H₂S or H₂S + CO₂. When the catalyst amount was increased to 4 g, the conversion of pure methane was about 90% at 800 °C, but 84% in the presence of H₂S and 80% in the presence of H₂S + CO₂. The poisoning by H₂S was irreversible at low temperatures but became reversible at higher temperatures. Since H₂S is adsorbed by the deposited carbon, the procedure for further removal of H₂S may be omitted. The coexistence of H₂S also affected the shape of the deposited carbon. Although carbon-based catalysts are known to be effective for methane decomposition in the presence of H₂S, iron oxide catalysts have the advantage of superior methane conversion at low temperatures. By flowing methane with CO₂ and H₂S from the downstream side after the reaction flowing from the upstream side for a certain period of time, the catalytic lifetime was drastically extended and the amount of hydrogen and solid carbon produced was dramatically increased, compared to the case of flowing from upstream all the way.     

Hydrogen production via methane decomposition on Raney-type catalysts

The catalytic decomposition of methane into hydrogen and carbon was studied on La₂O₃ doped Ni and Ni–Cu Raney-type catalysts. The activity and stability of the catalysts were assessed by comparing the experimental conversions with the calculated equilibrium conversions for each set of experimental conditions, and the maximum conversions with the conversions at the end of (at least) 5 h tests, respectively. Improved stability of La₂O₃ doped catalysts was ascribed to an electronic promotion effect. There is an optimum load of the promoter, which provides for extended periods of stable catalyst operation. The carbon deposits consist of carbon nanofibers and multiwall carbon nanotubes. The La₂O₃ doped Ni–Cu Raney-type catalysts presented in this work are remarkably efficient for the production of hydrogen by methane decomposition.     

Carbon-based nanocomposites in solid-state hydrogen storage technology: An overview

Hydrogen fuel is becoming a hot topic among the scientific community as an alternative energy source. Hydrogen is eco-friendly, renewable, and green. The synthesis and development of materials with great potential for hydrogen storage is still a challenge in research and needs to be addressed to store hydrogen economically and efficiently. Various solid-state materials have been fabricated for hydrogen energy storage; however, carbon-based nanocomposites have gained more attention because of its high surface area, low processing cost, and light weight nature. Carbon materials are easy to modify with various metals, metal oxides (MOs), and other organometallic frameworks because of the functional groups available on the surface and edges that increase the storage capacity of hydrogen. In addition, chemisorption is another way to enhance the hydrogen storage capacity of carbon-based nanocomposites. In this review, we discuss the success achieved thus far and the challenges that remain for the physical and chemical storage of hydrogen in various carbon-based nanocomposites. Various compositions of catalysts (eg, metal, MOs, alloy, metal organic frameworks) and carbon materials are designed for hydrogen storage. Superior energy storage in hybrids and composites as compared with pristine materials (catalysts or carbon nanotubes) is governed by the interaction, activation, and hydrogen adsorption/absorption mechanism of materials in the reaction profile. (Nano)composites comprising carbon material with metals, MOs, or alloys are important in this field, not only because of their potential for hydrogen sorption but also their significant cyclic stability and high efficiency upon successive adsorption-desorption cycles.     

Methane decomposition with some CO2 as co-feed: Co-production of syngas and carbon fibers/microspheres by using a hybrid of K2CO3 and coal char

Co-production of hydrogen and valuable carbonaceous materials by catalytic methane decomposition (CMD) is a promising process. However, nowadays it is still difficult for various carbon catalysts to make it. Here CMD with addition of some CO₂ as co-feed was proposed and evaluated by using a hybrid of K₂CO₃ and coal char (CC). Effect of the additional CO₂ as co-feed was investigated on methane conversion, the outlet gas composition, and the deposited carbon morphology. The results show that co-production of syngas (H₂ and CO) and carbon fibers/microspheres could be obtained along with high and stable methane (around 80%) and CO₂ conversion (up to about 100%) in the process. Stable molar ratios of H₂/CO (ranging from 0.6:1 to 5:1) as well as different carbon morphologies (amorphous, fibrous or microspherical) can be regulated and controlled by the molar ratio of CH₄/CO₂ (from 75:10 to 75:75) in the feedstock. Quantitative and qualitative analysis of the products show that there is probably a synergy between K₂CO₃ and CC during the reaction process.     

Production of hydrogen and carbon nanofibers through the decomposition of methane over activated carbon supported Pd catalysts

Hydrogen has been produced by decomposing methane thermocatalytically at 1123 K in the presence of activated carbon supported Pd catalysts (Samples coded as Pd5 and Pd10 respectively) procured from SRL Chemicals, India. The studies indicated that the Pd10 catalyst has higher catalytic activity and life for methane decomposition reaction at 1123 K and volume hourly space velocity (VHSV) of 1.62 L/hr?g. An average methane conversion of 50 mol % has been obtained for Pd10 catalyst at the above reaction conditions. SEM and TEM-EDXA images of Pd10 catalyst after methane decomposition showed formation of carbon nanofibers. XRD of the above catalyst revealed, moderately crystalline peaks of Pd which may be responsible for the increase in the catalytic life and the formation of carbon nanofibers.     

Joint-use of activated carbon and carbon black to enhance catalytic stability during chemical looping methane decomposition process

Chemical-looping methane decomposition using activated carbon as a catalyst has been considered a potentially promising approach for high-purity H₂ production with low cost and low CO₂ emission. However, activated carbon is known to deactivate fast despite its high initial catalytic activity. Oppositely, carbon black has shown stable catalytic methane decomposition that even increases slowly with time of reaction. Considering these two different activity trends, activated carbon and carbon black are jointly used to prepare catalysts and then test for the decomposition of the methane via chemical looping in this study that aimed to examine catalyst and reaction properties which may combine the high initial activity of activated carbon with the steady-and-increasing activity of carbon black. These mixed catalysts are examined using X-ray diffraction analysis (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS), Brunauer-Emmett-Teller (BET) and high-resolution transmission electron microscopy (HRTEM) before and after reaction testing to reveal chemical and physical constituents which contributed to their reactivities, and the mechanism of long catalytic activity has been discussed. The results point to insights and potential directions for modifying carbonaceous catalysts for chemical looping thermo-catalytic decomposition of methane.