Production of hydrogen by methane catalytic decomposition over Ni–Cu–Fe/Al2O3 catalyst

Catalysts with high nickel concentrations 75%Ni–12%Cu/Al₂O₃, 70%Ni–10%Cu–10%Fe/Al₂O₃ were prepared by mechanochemical activation and their catalytic properties were studied in methane decomposition. It was shown that modification of the 75%Ni–12%Cu/Al₂O₃ catalyst with iron made it possible to increase optimal operating temperatures to 700–750 °C while maintaining excellent catalyst stability. The formation of finely dispersed Ni–Cu–Fe alloy particles makes the catalysts stable and capable of operating at 700–750 °C in methane decomposition to hydrogen and carbon nanofibers. The yield of carbon nanofibers on the modified 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst at 700–750 °C was 150–160 g/g. The developed hydrogen production method is also efficient when natural gas is used as the feedstock. An installation with a rotating reactor was developed for production of hydrogen and carbon nanofibers from natural gas. It was shown that the 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst could operate in this installation for a prolonged period of time. The hydrogen concentration at the reactor outlet exceeded 70 mol%.     

Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of hydrogen and nanocarbon via methane decomposition

For the first time, simultaneous production of hydrogen and nanocarbon via catalytic decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investigated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the reaction activity remained almost unchanged during 1400 min steam on time at temperatures 540, 560 and 580 °C, respectively. The methane conversion level over these catalysts reached 60–75% with a 100% selectivity towards hydrogen. TEM observations revealed that most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used catalysts, keeping their exposed surface clean during the test and thus remaining active for continuous reaction without obvious deactivation. Two kinds of carbon materials, graphitic carbon (C_g) as major and amorphous carbon (C_A) as minor were produced in the reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nanotubes had an average diameter of approximately 30–50 nm and tens micrometers in length, depending on the reaction temperature, reaction time and Ni particle diameter. Four types of carbon nanofibers/nanotubes were detected and their formations greatly depend on the reaction temperature, time on steam and degree of the interaction between the metallic Ni and support. The respective mechanisms of the formation of nanocarbons were postulated and discussed.     

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.     

Ni–SiO2 and Ni–Fe–SiO2 catalysts for methane decomposition to prepare hydrogen and carbon filaments

Active and stable Ni–Fe–SiO₂ catalysts prepared by sol–gel method were employed for direct decomposition of undiluted methane to produce hydrogen and carbon filaments at 823 K and 923 K. The results indicated that the lifetime of Ni–Fe–SiO₂ catalysts was much longer than Ni–SiO₂ catalyst at a higher reaction temperature such as 923 K, however, a reverse trend was shown when methane decomposition took place at a lower reaction temperature such as 823 K. XRD studies suggested that iron atoms had entered into the Ni lattice and Ni–Fe alloy was formed in Ni–Fe–SiO₂ catalysts. The structure of the carbon filaments generated over Ni–SiO₂ and Ni–Fe–SiO₂ was quite different. TEM studies showed that “multi-walled” carbon filaments were formed over 75%Ni–25%SiO₂ catalyst, while “bamboo-shaped” carbon filaments generated over 35%Ni–40%Fe–25%SiO₂ catalysts at 923 K. Raman spectra of the generated carbons demonstrated that the graphitic order of the “multi-walled” carbon filaments was lower than that of the “bamboo-shaped” carbon filaments.     

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.     

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.     

New low cost mesoporous silica (MSN) as a promising support of Ni-catalysts for high-hydrogen generation via dry reforming of methane (DRM)

In this study, a new nano-sized mesoporous silica (MSN) as support for Ni-based catalysts was produced from natural resources and tested in the dry reforming of methane between 823 and 1023 K. The fresh and spent catalysts Ni-x/MSN (x = 5, 10 and 20 wt.%) were characterized by various techniques. All catalysts are selective for hydrogen production and exhibited long-term stability with low coke formation predominantly as carbon nanotubes, for Ni loadings less than 10% at 973 K. The catalytic results were correlated with the in situ generation of Ni nanoparticles which are highly dispersed on the MSN surface due to strong metal-support interactions thus preventing the sintering process. No significant deactivation was recorded along 25 h on stream meaning that the textural properties of the catalysts have not been altered by the coke deposition or reaction temperature. The prepared MSN is a potential support to be utilized for hydrogen generation.     

Hydrogen and multiwall carbon nanotubes production by catalytic decomposition of methane: Thermogravimetric analysis and scaling-up of Fe–Mo catalysts

Fe-based catalysts doped with Mo were prepared and tested in the catalytic decomposition of methane (CDM), which aims for the co-production of CO₂-free hydrogen and carbon filaments (CFs). Catalysts performance were tested in a thermobalance operating either at isothermal or temperature programmed mode by monitoring the weight changes with time or temperature, respectively, as a result of CF growth on the metal particles. Maximum performance of Fe–Mo catalysts was found at the temperature range of 700–900 °C. The addition of Mo as dopant resulted in an increase in the rate and amount of deposited carbon, reaching an optimum in the range 1.7–5.1% (mol) of Mo for Fe–Mo/Al₂O₃ catalysts, whereas for Fe–Mo/MgO catalyst an optimum at 5.1% Mo loading was obtained. XRD study revealed the effect of the Mo addition on the Fe₂O₃/Fe crystal domain size in the fresh and reduced catalysts. Tubular carbon nanostructures with high structural order were obtained using Fe–Mo catalysts, mainly as multiwall carbon nanotubes (MWCNTs) and bamboo carbon nanotubes. Fe–Mo catalysts showing best results in thermobalance were tested in a rotary bed reactor leading to high conversions of methane (70%) and formation of MWCNTs (5.3 g/h).     

Preferential oxidation of CO in a H2-rich stream over multi-walled carbon nanotubes confined Ru catalysts

Multi-walled carbon nanotubes (MWNTs) confined Ru catalysts were prepared by a modified procedure using ultrasonication-aided capillarity action to deposit Ru nanoparticles onto MWNTs inner surface. The structure properties of MWNTs supports and Ru catalysts were extensively characterized by XRD, TGA, H₂-TPR, XPS, TEM, FTIR and Raman spectra. The catalytic performance in the preferential oxidation of CO in a H₂-rich stream was examined in detail with respect to the influences of Ru loading, MWNTs diameter, various pretreatment conditions, and the presence of CO₂ and H₂O in the feed stream. In contrast with Ru catalysts supported on MWNTs external surface and other carbon materials, the superior activity was observed for the MWNTs-confined Ru catalyst, which was discussed intensively in terms of the confinement effect of carbon nanotubes. The optimized catalyst of 5 wt.% Ru confined in MWNTs with diameter of 8–15 nm can achieve the complete CO conversion in the wider temperature range and the favorable stability at 80 °C under the simulated reformatted gas mixture, which proves a promising catalyst for preferential CO oxidation in H₂-rich stream.     

Methane thermocatalytic decomposition to COx-free hydrogen and carbon nanomaterials over Ni–Mn–Ru/Al2O3 catalysts

Thermocatalytic decomposition of methane is proposed to be an economical and green method to produce CO_x-free hydrogen and carbon nanomaterials. In this work, the catalytic performance of Ni–Mn–Ru/Al₂O₃ catalyst under different reaction parameters (such as, pre-reduction temperature, reaction temperature, space velocity, etc.) were investigated to obtain optimum reaction conditions. The catalysts were characterized by N₂ adsorption/desorption, X-ray diffraction, inductively coupled plasma optical emission spectrometer and hydrogen temperature programmed reduction. For the 60 wt% Ni-5 wt% Mn-10 wt% Ru/Al₂O₃ catalyst using Ru(NO)(NO₃)_x(OH)_y(x + y = 3) as Ru precursor, the methane conversion rate obtained is high as 93.76% under optimum reaction conditions (reduction at 700 °C for 1 h, reaction at 750 °C, GSHV = 36,000 mL/g_cat h). Carbon nanomaterials formed during the process of methane thermocatalytic decomposition were characterized by scanning electron microscopy, thermal gravimetric analyzer and Raman spectroscopy. Carbon nanofibers were formed over all the Ni–Mn–Ru/Al₂O₃ catalysts.     

Non-supported bimetallic catalysts of Fe and Co for methane decomposition into H2 and a mixture of graphene nanosheets and carbon nanotubes

Herein, non-supported pure and mixed cobalt and iron oxide catalysts were synthesized from nitrate precursors using a simple, environmentally friendly preparation method in which water was the sole solvent. The prepared catalysts were then used to decompose methane into hydrogen and carbon (graphene nanosheets and carbon nanotubes). The fresh and spent catalysts were characterized by employing X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy-energy dispersive X-ray analysis (SEM/EDX), transmission electron microscopy (TEM) and N₂ adsorption-desorption techniques. In addition, the spent catalysts were subjected to thermo-gravimetric analysis (TGA) in order to measure the quantity of carbon deposits on the spent catalysts. The results indicated that the carbon deposited over these catalysts is a mixture of graphene nanosheets and carbon nanotubes (CNT). The results indicated that the mixed oxide catalysts exhibit higher catalytic activity than the pure oxides and that Fe: Co atomic ratio represents the key factor in the catalytic activity of these mixed oxides. After 420 min under the reaction feed, the 50Fe + 50Co catalyst shows the highest catalytic activity towards methane conversion of about 52.6% compared to 41.6% and 31.8% for 75Fe + 25Co and 25Fe + 75Co catalysts, respectively.     

Low-temperature catalytic conversion of greenhouse gases (CO2 and CH4) to syngas over ceria-magnesia mixed oxide supported nickel catalysts

Running dry reforming of methane (DRM) reaction at low-temperature is highly regarded to increase thermal efficiency. However, the process requires a robust catalyst that has a strong ability to activate both CH₄ and CO₂ as well as strong resistance against deactivation at the reaction conditions. Thus, this paper examines the prospect of DRM reaction at low temperature (400–600 °C) over CeO₂–MgO supported Nickel (Ni/CeO₂–MgO) catalysts. The catalysts were synthesized and characterized by XRD, N₂ adsorption/desorption, FE-SEM, H₂-TPR, and TPD-CO₂ methods. The results revealed that Ni/CeO₂–MgO catalysts possess suitable BET specific surface, pore volume, reducibility and basic sites, typical of heterogeneous catalysts required for DRM reaction. Remarkably, the activity of the catalysts at lower temperature reaction indicates the workability of the catalysts to activate both CH₄ and CO₂ at 400 °C. Increasing Ni loading and reaction temperature has gradually increased CH₄ conversion. 20 wt% Ni/CeO₂–MgO catalyst, CH₄ conversion reached 17% at 400 °C while at 900 °C it was 97.6% with considerable stability during the time on stream. Whereas, CO₂ conversions were 18.4% and 98.9% at 400 °C and 900 °C, respectively. Additionally, a higher CO₂ conversion was obtained over the catalysts with 15 wt% Ni content when the temperature was higher than 600 °C. This is because of the balance between a high number of Ni active sites and high basicity. The characterization of the used catalyst by TGA, FE-SEM and Raman Spectroscopy confirmed the presence of amorphous carbon at lower temperature reaction and carbon nanotubes at higher temperature.     

Tri-reforming of methane over Ni@SiO2 catalyst

A nickel-silica core@shell catalyst was applied for a methane tri-reforming process in a fixed-bed reactor. To determine the optimal condition of the tri-reforming process for production of syngas appropriate for methanol synthesis the effect of reaction temperature (550–750 °C), CH₄:H₂O molar ratio (1:0–3.0) and CH₄:O₂ molar ratio (1:0–0.5) in the feedstock was investigated. CH₄ conversion rate and H₂/CO ratio in the produced syngas were influenced by the feedstock composition. Increasing the amount of steam above the proportion of CH₄:H₂O 1:0.5 reduced the H₂:CO molar ratio in produced syngas to ∼1.5. Increasing oxygen partial pressure improved methane conversion to 90% at 750 °C. At low ∼550 °C reaction temperature the tri-reforming process was not effective with low hydrogen production (H₂ yield ∼20%) and very low <5% CO₂ conversion. Increasing reaction temperature increased hydrogen yield to ∼85% at 750 °C. From all the tested reaction conditions the optimal for tri-reforming over the 11%Ni@SiO₂ catalyst was: feed composition with molar ratio CH₄:CO₂:H₂O:O₂:He 1:0.5:0.5:0.1:0.4 at T = 750 °C. The results were explained in the context of characterisation of the catalysts used. The obtained results showed that the tri-reforming process can be applied for production of syngas with composition suitable for methanol synthesis.     

Effect of base promoter on activity of MCM-41-supported nickel catalyst for hydrogen production via dry reforming of methane

Dry reforming of methane (DRM) is considered a promising reforming technology that converts natural gas in the Natuna Sea into synthesis gas, which can be further utilized to produce beneficial chemicals such as olefins, alcohols, and liquid hydrocarbons. However, the challenges in commercializing the DRM process are carbon deposition and sintering of the catalyst at high temperatures, because of which the catalyst is easily deactivated. This study aimed to test the activity and stability of MCM-41-based catalysts for the DRM; determine the effect of promoter type on the activity and stability of MCM-41-based catalysts; and determine the effect of base promoter addition on the amount of carbon deposition. MCM-41-based catalysts were synthesized using incipient wetness impregnation method. XRD, N₂ Physisorption, H₂-TPR, CO₂-TPD, and TGA analysis were conducted to determine the physicochemical properties of the catalysts. The catalysts activity was tested in a fixed-bed reactor, under atmospheric pressure at 700 °C. Overall, all catalysts exhibited good stability for 240 min. Moreover, catalysts with Mg and Ca promoters showed the highest CH₄ and CO₂ conversion among all catalysts. Ni–Mg/MCM-41 catalyst yielded 72% CH₄ conversion and 54% CO₂ conversion, meanwhile Ni–Ca/MCM-41 yielded 69% CH₄ conversion and 55% CO₂ conversion. Furthermore, MCM-41-based catalysts with base promoter produced small amount of carbon deposition.     

Hydrogen production by methane decomposition using bimetallic Ni–Fe catalysts

The catalytic methane decomposition is the leading method for CO_x-free hydrogen and carbon nanomaterial production. In the present study, calcium-silicate based bimetallic Ni–Fe catalysts have been prepared and used to decompose the methane content of the ‘product gas’ obtained in the biomass gasification process for increasing total hydrogen production. Al₂O₃ was used as secondary support on calcium silicate based support material where Ni or Ni–Fe were doped by co-impregnation technique. The activity of catalysts was examined for diluted 6% methane-nitrogen mixture in a tubular reactor at different temperatures between 600 °C and 800 °C under atmospheric pressure, and data were collected using a quadrupole mass spectrometer. Catalysts were characterized by XRD, SEM/EDS, TEM, XPS, ICP-MS, BET, TPR, and TGA techniques. The relation between structural and textural properties of catalysts and their catalytic activity has been investigated. Even though the crystal structure of catalysts had a significant effect on the activity, a direct relation between the BET surface area and the activity was not observed. The methane conversion increased by increasing temperature up to 700 °C. The highest methane conversion has been obtained as 69% at 700 °C with F3 catalyst which has the highest Fe addition, and the addition of Fe improved the stability of catalysts. Moreover, carbon nanotubes with different diameter were formed during methane decomposition reaction, and the addition of Fe increased the formation tendency.     

Effect of calcination conditions on time on-stream performance of Ni/La2O3–ZrO2 in low-temperature dry reforming of methane

A series of catalysts based on Ni supported on mesoporous La₂O₃–ZrO₂ was prepared and tested in low-temperature (400 °C) dry reforming of methane for 100 h on stream. The catalysts were obtained from the same precursor by calcining in either flowing air or Ar at different temperatures. Both the temperature and the atmosphere had an effect on the catalytic activity and on-stream stability. With increasing calcination temperature, the dispersion of Ni decreased. Surprisingly, this resulted not in the lower, but in the higher intrinsic activity of Ni species. This increase can be rationalized by assuming that the rate-determining step is not CH₄ decomposition, but the removal of carbon deposits from Ni particle by reaction with CO₂. The catalysts calcined at 800 °C in Ar and air showed the strongest and the second strongest deactivation, respectively, caused by the formation of crystalline carbon coatings due to a lower number of CO₂ adsorption sites. The size of Ni particles favoring the formation of layered carbon species was found to be the main origin of the catalysts deactivation in the low-temperature dry reforming of methane.     

Steam reforming of acetic acid in the presence of Ni coated with SiO2 microsphere catalysts

Steam reforming of acetic acid was investigated in the presence of Ni@SiO₂ microsphere catalysts. The effects of Ni loading, H₂O/AcOH ratio, and temperature on hydrogen selectivity and acetic acid conversion were determined via statistical analysis. Results indicated the dependence of parameters on hydrogen selectivity.The stable activity observed for the reaction conducted at 2.5H₂O/AcOH ratio and 750 °C implied future utilization potential of the catalyst for time on stream experiments despite the inevitable coke formation. Boudard reaction and methane decomposition, known as possible carbon sources, was ruled out due to the opposite trends between CO₂ and CO selectivities and mitigation of methanation reactions. The ambiguous pattern of conversions observed for varying H₂O/AcOH implied the presence of a different reaction path leading to consecutive ketonozation of acetic acid and aldol-condensation of acetone as the primary sources of carbon deposition.     

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.     

Hydrogen production by catalytic methane decomposition over yttria doped nickel based catalysts

Catalytic methane decomposition can become a green process for hydrogen production. In the present study, yttria doped nickel based catalysts were investigated for catalytic thermal decomposition of methane. All catalysts were prepared by sol-gel citrate method and structurally characterized with X-ray powder diffraction (XRD), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and Brunauer, Emmet and Teller (BET) surface analysis techniques. Activity tests of synthesized catalysts were performed in a tubular reactor at 500 ml/min total flow rate and in a temperature range between 390 °C and 845 °C. In the non-catalytic reaction, decomposition of methane did not start until 880 °C was reached. In the presence of the catalyst with higher nickel content, methane conversion of 14% was achieved at the temperature of 500 °C. Increasing the reaction temperature led to higher coke formation. Lower nickel content in the catalyst reduced the carbon formation. Consequently, with this type of catalyst methane conversion of 50% has been realized at the temperature of 800 °C.     

Microwave-enhanced methane cracking for clean hydrogen production in shale rocks

Steam methane reforming (SMR) generates about 95% of hydrogen (H₂) in the U.S. using natural gas as a main feedstock. However, this technology also generates a large amount of carbon dioxide (CO₂), a major greenhouse gas causing global warming. Carbon capture and storage (CCS) technique is required, but the cost and safety of storing CO₂ underground are a concern. Here we propose a new approach using microwave/electromagnetic irradiation to produce clean hydrogen from unrecovered hydrocarbons within petroleum reservoirs. Solid carbon or CO₂ produced during this process will be simultaneously sequestrated underground without involving CCS. In this paper, we perform a series of experiments to investigate the in-situ hydrogen production from shale gas (methane) conversion by passing a methane stream through a packed shale rock sample heated by microwave. We found that methane conversion was significantly enhanced in the presence of Fe and Fe₃O₄ particles as catalysts, with a conversion of 40.5% and 100% at reaction temperature of 500 °C and 600 °C, respectively. Methane conversion is promoted at a lower reaction temperature by the catalytic effect of minerals in shale. Additionally, the influences of catalysts, shale rock, and methane flow rate are characterized.