Natural sand as a non-conventional catalyst for hydrogen production by methane thermo-catalytic decomposition

The thermo-catalytic decomposition of methane is considered a promising process for H₂ production in the carbon constrained world. A durable and cost-effective catalyst is required for practical methane decomposition processes within industrial applications; unfortunately, most catalysts suffer from extensive deactivation because of carbon deposition. To address this issue, this study assessed a low-cost, widely-available material - natural sand - as a non-conventional catalyst with the realization that it contained impurities such as iron oxides which may impart reaction activity. Its interesting performance in the methane decomposition reaction is reported herein and assessed relative to a potential cause of increasing catalytic activity with longer reaction times. One result of possible significance is the development of tubular carbon structures on the sand's surface that grew significantly in diameter and length with longer reaction times. High Resolution Transmission Electron Microscopy (HRTEM) imaging showed that this tubular carbon contained extensive humps on the external surface of the tube walls which grew in prominence with longer reaction times. The humps did not contain iron particles, in contrast to the heads of the tubes, and consisted of highly disordered graphitic layers. Previous research has pointed to the existence of free radicals or unsaturated bonding in these types of disordered layers, which can provide sites for catalytic reactions. Hence, it is proposed that the increasing prominence of the humps as the reaction time was increased, and by extension an increasing number of surface free radicals, was a possible cause for an increasing catalytic activity after the iron particles on the sand surface were covered with carbon and tube growth was initiated. These data are seen as potentially useful for devising alternative approaches to diminish catalytic deactivation during methane conversion to H₂.     

Hydrogen Production by Thermocatalytic Methane Decomposition

This article reports on the use of mesoporous carbons as catalysts for hydrogen production by thermocatalytic decomposition of methane. The prepared ordered mesoporous carbons (OMCs) and commercial carbon materials (including disordered microporous carbon, mesoporous carbon, and carbon nanotube) were tested for their catalytic activities for methane decomposition in a fixed-bed reactor. Characterizations by different techniques including gas adsorption, x-ray photoelectron spectroscopy, and transmission electron microscopy were carried out for the pristine and used catalysts. Results showed that the initial activity was related to the chemical structure of the catalysts such as defects, while the long-term activity was related to the physical characteristics such as the BET surface area and pore volume. Unlike disordered carbons, OMCs with relatively larger uniform pores could maintain a steady catalytic activity for a longer time, followed by a sharp activity decline due to the blockage of most of the pores. It is conceived that by designing and preparing carbon materials with ideal pore systems using the replication method, it is possible to enhance the catalytic activity and stability of the reaction.     

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.     

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.     

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.     

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.     

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.     

Thermo-catalytic decomposition of propane over carbon black in a fluidized bed for hydrogen production

Thermo-catalytic decomposition of propane to solid carbon and hydrogen was examined for hydrogen production without CO₂ emission. The reaction was carried out over a carbon black catalyst in a bench-scale fluidized bed reactor. Effects of reaction temperature on the propane conversion and product distribution were examined. Catalytic activity of the carbon black was maintained stable for longer than 8 h in spite of carbon deposition. From 600 to 650 °C, the propane conversion increased sharply with propylene produced in a considerably larger amount than methane. As the reaction temperature further increased up to 800 °C, the major hydrocarbon product was methane; the production of propylene decreased rapidly and ethylene was the next most abundant product. The surface area of the carbon black was decreased as the reaction proceeded due to carbon deposition. Surface morphology of the used carbon black was observed by TEM and the change of the aggregates size was measured.     

The effect of ethanol on carbon-catalysed decomposition of methane

Because of its ecological character, the reaction of catalytic decomposition of methane (CDM) is expected to be an important future method of hydrogen generation. However, the main drawback of this technology is a relatively fast deactivation of the catalyst used, as a consequence of its pores blocking by the low-active methane-originated carbon deposit. This paper reports on an attempt of restricting the catalyst deactivation by introducing into the reaction system ethyl alcohol capable of forming in situ a potentially active in this reaction carbonaceous deposit. The catalyst used was activated carbon obtained from the waste material (hazelnut shells). The reactions of methane and ethanol decomposition were performed by the alternate method (for certain time methane was introduced into the reactor, and then it was replaced by ethanol). Three temperatures of the reactions were applied (750, 850 or 950 °C) and another variable was the duration of the ethanol decomposition. As follows from the results, an addition of ethanol has diverse effect on the catalytic activity of activated carbon and the amount of hydrogen formed depends on the temperatures of methane and ethanol decompositions and on the time of the reagent dosing.     

Methane decomposition kinetics and reaction rate over Ni/SiO2 nanocatalyst produced through co-precipitation cum modified Stöber method

Co-precipitation cum modified Stöber method was adopted to produce nano-Ni/SiO₂ (n-Ni/SiO₂) catalyst and conducted a series of methane decomposition kinetic experiments in a fixed bed pilot plant. Methane decomposition activity of n-Ni/SiO₂ catalyst was quantified by considering thermodynamic deposition of carbon at a temperature range of 550–650 °C and methane partial pressure from 0.2 to 0.8 atm. The utmost methane conversion of 18.87 mmol/g_cat min was obtained at 650 °C and methane partial pressure of 0.8 atm. The findings concluded that the enhancement occurred with carbon formation rate when increasing the methane partial pressure is very much evident at higher temperature such as 650 °C. However, the intensity in methane decomposition descending tendency was declined at lower reaction temperature. The effects of methane partial pressure and reaction temperature on the specific molar carbon formation rate were also examined. The calculated reaction order and activation energy were 1.40 and 61.1 kJ mol^?1, respectively. The kinetic experiments showed the existence of an optimum reaction condition to achieve the highest performance of n-Ni/SiO₂ catalyst in terms of methane decomposition rate. However, carbon accumulation ceases once complete catalyst deactivation occurred at certain reaction conditions such as high temperature and lower methane partial pressure. Virgin nanocatalyst and as-produced nanocarbons were studied with BET, XRD, and TEM.     

Kinetic modeling of hydrogen production by thermal decomposition of methane

A kinetic model for the thermal decomposition of methane was developed by modifying a model for soot formation in combustion. The modifications consisted of adding five reactions representing surface chemistry on carbon particles. One kinetic parameter for the new surface reactions was fit to experimental data and the other parameters were determined by analogy to known gas-phase reactions. The modified model reproduces well the hydrogen concentrations at the beginning and end of recent experiments on the thermal decomposition of methane in the presence of carbon catalysts. The model predicts that increasing the pressure from 0.1 to 3.0 MPa will decrease hydrogen production with carbon catalysts by 48–60%. This prediction is robust to variations in the rate constants for the surface reactions and the rate constant for a key gas-phase reaction.     

Decomposition of methane in the presence of ethanol over activated carbon catalyst

The interest in hydrogen as a potential fuel of the future has stimulated development of new technologies of its production. The main method of hydrogen production is based on the process of steam reforming of methane, but recently increasing attention has been paid to the catalytic decomposition of methane (CDM) whose advantage is its pro-ecological character. This reaction, besides hydrogen, produces also catalytically low-active carbonaceous deposit which settles on the surface of the catalyst and leads to its deactivation. The study reported is an attempt at suppressing the catalyst deactivation by developing a method leading to formation of carbonaceous deposit potentially active in CDM process. For this purpose, it was proposed that the reaction system would contain methane and ethanol. Simultaneous decomposition of these two substances was performed in parallel at three temperatures of 750, 850 or 950 °C. The catalyst was activated carbon obtained from the hazelnut shells. The addition of ethanol was found to have a positive effect on the course of CDM, leading to an increase in the amount of hydrogen produced and to stabilisation of the catalyst activity at a high level.     

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.     

Tailored hydrotalcite-based Mg-Ni-Al catalyst for hydrogen production via methane decomposition: Effect of nickel concentration and spinel-like structures

Thrive for the CO_x-free hydrogen production via methane decomposition has gained much interest owing to its feasibility and environmental friendliness. Herein, ahydrotalcite based Nickel catalyst was synthesized via co-precipitation method by varying the amount of Nickel concentration and tested for methane decomposition reaction in a fixed bed reactor. In addition, the effect of calcination temperature in the development of the spinel-like structure of as-developed catalyst was comprehensively discussed. It was found that the hydrotalcite based Nickel catalyst prepared at 40% Nickel concentration has the highest performance of above 80% conversion for 7 h of methane decomposition which was owing to its effective diffusion of carbon particles and its spinel-like structure, evidently from the XRD and FESEM analysis. The profound performance monitored here was attributed to the formation of carbon nanofibers (CNFs) on the surface of the catalyst which levitates the active Ni^ospecies on its tips, results in more available active sites for the chemisorptions of the methane molecules. Nevertheless, the excessive of Nickel concentration leads to the detrimental methane decomposition performance, hencepromotes the formation of large particle size and successive development of bulk NiO phases during the reduction process, consequently abnegate the overall methane decomposition reaction. The aforementionedfindingsshow that the spinel-like structure is the key factor in the growth of long uniform CNFs and elevation of active sites on the fibre tips.     

Influence of space velocity and catalyst pretreatment on COx free hydrogen and carbon nanotubes production over CoMo/MgO catalyst

The influence of catalyst pretreatment and space velocity in methane decomposition into COx-free hydrogen and carbon nanotubes were investigated over CoMo/MgO catalyst. The reduction of catalyst before methane decomposition leads to a hydrogen production without significant formation of COx (concentration lower than 5 ppm after 25 min of reaction) suitable for its use in fuel cells. However, a high hydrogen space velocity in the pretreatment increased the rate of catalyst deactivation. The CO and CO₂ formation rates showed a common trend for all conditions tested: there was a high initial rate and, after 2 min of reaction, there was a lower stabilized rate. The increase in methane space velocity increased the hydrogen formation rate and the degree of carbon nanotubes graphitization. However, it strongly decreases methane conversion, as expected. The use of low hydrogen space velocity, 0.25 h⁻¹, in catalyst pretreatment and high methane space velocity, 8 h⁻¹, in reaction step, provided the highest hydrogen yield and well-structured carbon nanotubes.     

Catalytic methane decomposition over activated carbons prepared from direct coal liquefaction residue by KOH activation with addition of SiO2 or SBA-15

Activated carbons (ACs) are of good potential to be the catalysts for methane decomposition to produce hydrogen without CO and CO₂. Coal liquefaction residue (CLR) seems to be a promising precursor for ACs. In this work, several types of ACs were prepared by KOH activation from Shenhua CLR with addition of SiO₂ or SBA-15. The catalytic activity and stability for methane decomposition were investigated and compared with commercial coal-based AC and carbon black (BP2000). The results show that the prepared ACs have larger surface area, narrower pore distribution, and higher catalytic activity than those directly prepared by KOH activation, and are superior to the commercial carbons. The increased microporosity resulting from the soluble salts formed by the reaction between the additive and KOH is responsible for the high catalytic activity.     

Natural Fe-based catalysts for the production of hydrogen and carbon nanomaterials via methane decomposition

Tierga and Ilmenite Fe-based ores are studied for the first time in the catalytic decomposition of methane (CDM) for the production of carbon dioxide-free hydrogen and carbon nanomaterials. Tierga exhibits superior catalytic performance at 800 °C. The effect of the reaction temperature, space velocity and reducing atmosphere in the catalytic decomposition of methane is evaluated using Tierga. The highest stability and activity (70 vol% hydrogen concentration) is obtained at 850 °C using methane as a reducing agent. Reduction with methane causes the fragmentation of the iron active phase and inhibits the formation of iron carbide, improving its activity and stability in the CDM. Hybrid nanomaterials composed of graphite sheets and carbon nanotubes with a high degree of graphitization are obtained. Considering its catalytic activity, the carbon quality, and the low cost of the material, Tierga has a competitive performance against synthetic iron-catalysts for carbon dioxide-free hydrogen and solid carbon generation.     

Hydrogen production by propylene-assisted decomposition of methane over activated carbon catalysts

Catalytic decomposition of methane (CDM) permits obtaining hydrogen in high yields and – what is essential – it does not lead to release of CO₂. Unfortunately, most of the catalysts used in this process undergo fast deactivation. Their possible regeneration, consisting in the removal of pore blocking carbonaceous deposit of low catalytic activity, leads to generation of undesirable carbon dioxide. An alternative solution for maintaining high catalyst activity in the CDM reaction can be generation of the catalytically active carbonaceous deposit on its surface. Such a deposit can be obtained by decomposition of different organic substances. This paper reports on methane decomposition carried out in the presence of propylene (used in the concentration of 10 or 20%). The reaction was performed at three temperatures of 750 °C, 850 °C or 950 °C. Three types of activated carbon were tested as catalysts: the first one was obtained by activation of pine wood biomass with Na₂CO₃, whereas the second and third ones were commercial carbons (WG-12 and Norit RX3 Extra). According to the results, the addition of propylene to the CDM system effectively reduces deactivation of the activated carbon catalysts and permits fast stabilisation of their catalytic activity at a high level.     

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.     

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.