Modelling of one-dimensional heterogeneous catalytic steam methane reforming over various catalysts in an adiabatic packed bed reactor

Kinetic data relevant to steam methane reforming (SMR) are often applied to catalysts and conditions for which they have not been derived. In this work, kinetic rates for the two SMR and water gas shift reactions were derived for 12 commonly used reforming catalysts based on conversion data obtained from the literature. Subsequently, these rates were tested in dynamic operation, steady-state, and equilibrium using a 1-D reactor model developed in-house with gPROMS model builder. Modelling outputs were further validated independently at equilibrium using the software chemical equilibrium with applications (CEA), and the literature. The effect of variables such as temperature, pressure, steam to carbon ratio (S/C), and gas mass flux (G_s) on the performance of the SMR process was then studied in terms of fuel and steam conversion (%), H₂ purity (%), H₂ yield (wt. % of CH₄) and selectivity of the carbon-based products. A comparative study was then performed for the 12 catalysts. Some catalysts showed better activity owing to their fast kinetics when they are tested in mild industrial conditions, while others performed better in more severe industrial conditions, substantiating that the choice of a catalyst ought to depend on the operating conditions.     

Ni supported on MgO modified attapulgite as catalysts for hydrogen production from glycerol steam reforming

A series of Mg-modified Ni/Attapulgite (ATP) catalysts have been prepared by impregnation method for glycerol steam reforming to produce hydrogen. The physicochemical properties of catalysts were characterized using various techniques including N₂ physical adsorption analysis, XRD, H₂-TPR, SEM, TEM and NH₃-TPD. The results of N₂ physical adsorption indicated MgO modified Ni-based catalysts had unique mesostructure, resulting in the high metal dispersion and interaction between active metal and support as proven by XRD, TEM and H₂-TPR. Results of glycerin reforming experiments showed that Ni/10MgO/ATP catalyst had the highest activity than that of the other catalysts. Ni/10MgO/ATP catalyst had the smallest Ni average crystal size (10.1 nm) and the highest surface area (110.31 m²/g). These excellent properties made it show the enhanced glycerol conversion (94.71%) and a higher H₂ yield (88.45%) and the longest stability (30 h) during glycerol steam reforming (GSR) at 600 °C, W/G = 3, and WHSV = 1 h^?1. The used catalysts after 60 h of glycerin reforming experiments were also investigated by XRD, SEM, TEM, Roman and TG-DTG. The results indicated that the addition of Mg significantly inhibited the sintering of nickel grains and the formation of amorphous carbon. Therefore, Ni/10MgO/ATP catalyst increased the activity of the catalyst and extended the life of the catalyst.     

Comparative study of fuel gas production for SOFC from steam and supercritical-water reforming of bioethanol

Theoretical study of fuel gas (H₂ + CO) production for SOFC from bioethanol was carried out to compare performances between two reforming technologies, including steam reforming (SR) and supercritical-water reforming (SCWR). It demonstrates that the fuel gas productions are comparable among the two reforming systems; however, SCWR requires the operation at much higher temperature and pressure than SR. The maximum hydrogen yield can be obtained at 850 K, atmospheric pressure, ethanol to water molar feed ratio of 1:20 for SR system and at 1300 K, 22.1 MPa, and ethanol to water feed ratio of 1:20 for SCWR. The use of a distillation column to purify the bioethanol feed was proven to improve the fuel conversion efficiency of both systems. The analysis reveals that SCWR is a promising system for fuel production for SOFC when a gas turbine is incorporated to the system for energy recovery. Further, it is not necessary to distil bioethanol to obtain too high ethanol recovery (i.e. >90%) as higher energy consumption at the distillation column could lead to lower overall thermal efficiency.     

Thermodynamic analysis of ethanol/water system with the stoichiometric method

An analysis of the chemical equilibrium of ethanol/water system, using the stoichiometric method, has been performed. Intermediate compounds and coke formation are analyzed.     

Thermodynamic and experimental study of combined dry and steam reforming of methane on Ru/ ZrO2-La2O3 catalyst at low temperature

Analysis of the effect of adding small amounts of steam to the methane dry reforming feed on activity and products distribution was performed from thermodynamic equilibrium calculations of the system based on the Gibbs free energy minimization method. This analysis is supported by new insights from the direct experimental investigation of the influence of co-feeding with H₂O over a Ru/ZrO₂-La₂O₃ catalyst. Activity measurements were carried out in a fixed-bed reactor but using the operating conditions applicable in a Pd membrane reactor, that is, at maximum reaction temperature below 550 °C. Experimental results were in good agreement with thermodynamics predictions. It was observed that the addition of H₂O into the dry reforming feed strongly affects activity and products distribution. The co-feeding of steam resulted in increasing methane conversion and hydrogen yield but decreasing carbon dioxide conversion and carbon monoxide yield. At a given temperature, syngas composition (H₂/CO ratio) can be tuned by changing the amount of H₂O co-fed. Interestingly the stability of the Ru/ZrO₂-La₂O₃ catalyst was improved by adding steam to the dry reforming reactant mixtures.     

Synthesis,characterization, and catalytic activity of Ni/CeMnO2 catalysts promoted by copper,cobalt, potassium and iron for ethanol steam reforming

Steam reforming of ethanol on CeMnO₂-supported Ni with various promoters (Cu, Co, K and Fe) was studied to hydrogen generation in this work. Support was prepared by co-precipitation method. Active metal and promoters were added by impregnation method. Samples were analyzed by BET, XRD, TPR, TPD, TGA, SEM and EDX. Higher conversion was obtained in the samples promoted by Cu and Fe. The catalyst promoted by Fe showed the highest hydrogen yield because of conducting the reaction to dehydrogenation route. Ni–Fe/CeMnO₂ also exhibited good stability during 20 h. CO selectivity decreased in the Co-promoted sample compared the others due to the effective role of Co in progress of water-gas shift reaction. Unaccepted performance of K-promoted sample was resulted from low specific surface area and also reduction of Ni dispersion on the surface of the sample with K.     

Dry reforming of methane over Ni/MgO–Al2O3 catalysts: Thermodynamic equilibrium analysis and experimental application

In this study, dry reforming of methane (DRM) employing a Ni/MgO–Al₂O₃ catalyst was undertaken to evaluate the effects of temperature (650, 700 and 750 °C), weight hourly space velocity (7.5, 15 and 30 L h⁻¹ g_cat⁻¹) and catalyst MgO content (3, 5 and 10 wt%) on catalytic activity and coke-resistance. The catalysts were prepared by the wet impregnation method and were characterized by wavelength dispersive X-ray fluorescence (XRF), N₂ physisorption, X-ray diffraction (XRD), temperature-programmed reduction (TPR-H₂), temperature-programmed desorption (TPD-NH₃), H₂ chemisorption, thermogravimetric/derivative thermogravimetry analysis (TG/DTG) and scanning electron microscopy (SEM). The best conversions of methane (CH₄) and carbon dioxide (CO₂) and lower coke formation were obtained using higher temperatures, lower WHSV and 5 wt% MgO in the catalyst. The H₂/CO molar ratios obtained were within the expected range for the DRM reaction. The experimental yields of H₂ and CO differed from chemical equilibrium, mainly due to occurrence of the reverse water-gas shift reaction. Thermodynamic analysis of the reaction system, based on minimization of the Gibbs free energy, was performed in order to compare the experimental results with the optimal values for chemical equilibrium conditions, which has indicated that the DRM reaction was favored by higher temperature, lower pressure, and lower CH₄/CO₂ molar ratio.     

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

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

Synthesis of a new self-supported Mgy(CuxNi0.6-xMn0.4)1-yFe2O4 oxygen carrier for chemical looping steam methane reforming process

Novel self-supported Mg_y(Cu_xNi_0.6-xMn_0.4)_1-yFe₂O₄ with (y = 0, 0.05, 0.1, 0.15, and x = 0, 0.15, 0.3, 0.45, 0.6) oxygen carriers (OCs) are synthesized through the co-precipitation method. The synthesized OCs’ properties are characterized by X-ray powder diffraction (XRD), Raman spectra, transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), and Thermogravimetric Analysis (TGA). The synthesized OCs are assessed in Chemical Looping Steam Methane Reforming (CL-SMR) process subject to different mesh sizes, reaction temperatures, Steam/Carbon (S/C) molar ratios, Mg concentrations, and Cu and Ni concentrations. The characterization of the OCs and process results indicate the contributive effect of Mg incorporation on the Cu_xNi_0.6-xMn_0.4Fe₂O₄ support structure. The redox results reveal that Mg_0.1(Cu_0.3Ni_0.3Mn_0.4)_0.9Fe₂O₄ OC is of the highest activity, even at low reduction temperatures. This OC exhibits the highest activity and stability with lowest coke deposition during 24 redox cycles at 650 °C and S/C = 2.5. The highest CH₄ conversion of about 99.4% and H₂ yield of about 84.4% are obtained.     

Hydrogen production from bio-oil: A thermodynamic analysis of sorption-enhanced chemical looping steam reforming

The steam reforming of pyrolysis bio-oil is one proposed route to low carbon hydrogen production, which may be enhanced by combination with advanced steam reforming techniques. The advanced reforming of bio-oil is investigated via a thermodynamic analysis based on the minimisation of Gibbs Energy. Conventional steam reforming (C-SR) is assessed alongside sorption-enhanced steam reforming (SE-SR), chemical looping steam reforming (CLSR) and sorption-enhanced chemical looping steam reforming (SE-CLSR). The selected CO₂ sorbent is CaO(s) and oxygen transfer material (OTM) is Ni/NiO. PEFB bio-oil is modelled as a surrogate mixture and two common model compounds, acetic acid and furfural, are also considered. A process comparison highlights the advantages of sorption-enhancement and chemical looping, including improved purity and yield, and reductions in carbon deposition and process net energy balance.The operating regime of SE-CLSR is evaluated in order to assess the impact of S/C ratio, NiO/C ratio, CaO/C ratio and temperature. Autothermal operation can be achieved for S/C ratios between 1 and 3. In autothermal operation at 30 bar, S/C ratio of 2 gives a yield of 11.8 wt%, and hydrogen purity of 96.9 mol%. Alternatively, if autothermal operation is not a priority, the yield can be improved by reducing the quantity of OTM. The thermodynamic analysis highlights the role of advanced reforming techniques in enhancing the potential of bio-oil as a source of hydrogen.     

Thermodynamic analysis of ethanol steam reforming using Gibbs energy minimization method: A detailed study of the conditions of carbon deposition

In this paper, a thermodynamic analysis of ethanol/water system, using the Gibbs energy minimization method, has been carried out. A mathematical relationship between Lagrange's multipliers and carbon activity in the gas phase was deduced. From this, it was possible to calculate carbon activities in both stable and metastable systems. For the system that corresponds to ethanol steam reforming at very low contact times, composed mainly of ethylene and acetaldehyde, carbon activities were always much greater than unity over the whole temperature range, changing from 1.2 × 10⁷ at 400 K to 1.1 × 10⁴ at 1200 K. Furthermore, there was practically no effect of the inlet steam/ethanol ratio on carbon activity values. These results indicate that such a system is highly favorable to carbon formation. On the other hand, by considering a more stable system, in order to represent high contact times, it was observed that carbon activities are much lower and depend greatly on the inlet steam/ethanol ratio employed. Besides, the complete conversion of ethylene and acetaldehyde into other species, such as CO, CO₂, CH₄ and H₂, lowers the total Gibbs energy of the system. By computing carbon activities in experimental systems, it was also possible to explain deviations between thermodynamic analysis and experimental results regarding carbon deposition.     

Methanol steam reforming integrated with oxidation in a conical annulus micro-reactor

A micro-channel reactor with circular cross section was numerically studied. Inside the inner cylinder and the annulus section, steam reforming and oxidation reactions were occurred, respectively. With the variation in diameter of the annulus section along the reactor length, the effect of diameter changing was also studied. In this case, outer section is an incomplete cone. The results showed that conical annulus (right inlet) micro-reactor (when the diameter of the cone decreased along the reactor length) represents higher temperatures and conversions. Then, influences of some parameters were considered in this micro-reactor. With increasing some parameters such as inlet temperature and the steam to carbon ratio of inlet flow, methanol conversion increases, and increasing some other parameters such as flow rate, solid thickness and porosity of bed leads to the methanol conversion decreases as well. Effect of various diameters in this micro-reactor was considered. Also when oxidation reaction happened inside outer cone, the better results was represented.     

A heterogeneous dynamic model for the simulation and optimisation of the steam methane reforming reactor

In the current paper the dynamic behaviour of an industrial heterogeneous catalytic packed-bed reactor for the steam reforming of methane is examined. The model consists of a set of partial differential equations describing the physico-chemical processes that take place both in solid and gas phases accounting for diffusional limitations within the catalyst particles. The model was validated against literature data, while the heat provided to the reactor wall was optimised in terms of the optimal H₂ yield using a quadratic wall temperature profile. The values of the physico-chemical properties were adjusted to the severe operating conditions (high pressures and temperatures) of the reactor accounting for multicomponent gas mixture properties. It is shown that the 2-phase reactor concept along with the optimised wall temperature profile capture very well the dynamic conversion, the temperature and the partial pressure profiles both at bed and at particle level.     

CuFeO2–CeO2 nanopowder catalyst prepared by self-combustion glycine nitrate process and applied for hydrogen production from methanol steam reforming

Hydrogen (H₂) is being considered as an alternate renewable energy carrier due to the energy crisis, climate change and global warming. In the chemical industry, hydrogen production is mainly accomplished by the steam reforming of natural gas. In the present study, CuFeO₂–CeO₂ nanopowder catalyst with a heterogeneous delafossite structure was prepared by the self-combustion glycine nitrate process and used for steam reforming of methanol (SRM). The precursor solution was fabricated from Cu–Fe–Ce metal-nitrate mixed with glycine and an aqueous solution. The prepared CuFeO₂–CeO₂ nanopowder catalyst was studied by different physical and chemical characterization techniques. The prepared CuFeO₂–CeO₂ nanopowder catalyst was immensely porous with a coral-like structure. The BET surface area measurement revealed that the specific surface area of as-combusted CuFeO₂–CeO₂ nanopowder varied from 5.6248 m²/g to 19.5441 m²/g. In addition, the production rate of CuFeO₂–CeO₂ was improved by adding CeO₂ and adjusting the feeding rate of the methanol. The highest H₂ generation rate of the CuFeO₂–CeO₂ catalyst was 2582.25 (mL STP min⁻¹ g-cat⁻¹) at a flow rate of 30 sccm at 400 °C. Hence, the high specific surface area of the 70CuFeO₂–30CeO₂ nanopowder catalyst and the steam reforming process could have a very important industrial and economic impact.