Gibbs free energy minimization as a way to optimize the combined steam and carbon dioxide reforming of methane

Gibbs free energy minimization was applied to study thermodynamic equilibrium of the combined steam and carbon dioxide reforming of methane. Coke deposition, the content of methane and carbon dioxide in syn-gas as well as H₂/CO ratio were investigated as a function of CO₂/CH₄ and H₂O/CH₄ mole ratios at different temperatures and pressures. The ranges of the molar ratios CH₄/CO₂/H₂O in the feed with H₂/CO = 2.1-2.2 were identified at which reforming of methane is not complicated by coke deposition. For each range optimized CH₄/CO₂/H₂O molar ratios characterized by the lowest content of methane and carbon dioxide in syn-gas were found.     

Modeling and analysis of ceramic-carbonate dual-phase membrane reactor for carbon dioxide reforming with methane

A new high temperature tube-shell membrane reactor (MR) design for separation and utilization of CO₂ from the flue gas and for simultaneous production of syngas through carbon dioxide reforming of methane (CRM) is reported. The MR is based on a dual-phase CO₂ permeation membrane consisting of mixed-conducting oxide and molten carbonate phases. High temperature CO₂-containing flue gas and CH₄ are respectively fed into the shell and tube sides of the reactor packed with a reforming catalyst. Under performance conditions, CO₂ permeates selectively through the membrane from the shell side to the tube side and reacts with CH₄ to produce syngas. Additionally, the heat from the flue gas can transfer directly through the membrane to provide energy for the endothermic CRM reaction. An isothermal steady-state model was developed to simulate and analyze CRM in the MR in this work. The effect of the design and operational parameters, such as inlet CH₄ flow rate, shell side CO₂ partial pressure and the flue gas composition, i.e., containing O₂ or not, as well as the membrane thickness on the reactor performance with respect to the CH₄ conversion and the CO₂ permeation flux were investigated and discussed. The results show that the MR has a high efficiency in separating and utilizing CO₂ from the flue gas. For a CH₄ space velocity of 3265.31 h⁻¹, with a membrane thickness of 0.075 mm and the shell side CO₂ partial pressure of 1 atm, a CH₄ conversion of 48.06% and an average CO₂ permeation flux of 1.52 mL(STP) cm⁻² min⁻¹ through the membrane tube at 800 °C are obtained. Further improvement of the MR performance can be achieved by involving O₂ in the permeation process.     

Transient reaction and exergy analysis of catalytic partial oxidation of methane in a Swiss-roll reactor for hydrogen production

Catalytic partial oxidation of methane (CPOM) is a promising method for hydrogen production with autothermal reaction. To figure out the unsteady reaction characteristics of CPOM in a Swiss-roll reactor along with heat recirculation, a numerical method is employed to simulate the transient reaction dynamics, with emphasis on energy recovery using exergy analysis. Three different gas hourly space velocities (GHSVs) of 5000, 10,000 and 50,000 h⁻¹ with the condition of atomic O/C ratio of 1 are considered. The predictions indicate that increasing GHSV substantially shortens the transient period of chemical reactions; however, it also reduces the methane conversion, as results of more reactants sent into the reactor and shorter residence time of the reactants in the catalyst bed. Within the investigated range of GHSV, the methane conversion with energy recovery at the steady state is larger than 80%, much higher than the reaction without heat recovery. The selectivities of H₂ and CO in the product gas are always larger than 90%. The exergy recovery is in the range of 66–80%, implying that over two-third useful work contained in the product gas can be reused to preheat the reactants in the reactor, thereby enhancing the performance of CPOM.     

Entropy generation from hydrogen production of catalytic partial oxidation of methane with excess enthalpy recovery

Catalytic partial oxidation of methane (CPOM) is an important route for producing hydrogen and it is featured by autothermal reaction. To recognize the reaction characteristics of CPOM, H₂ production and entropy generation from CPOM in Swiss-roll reactors are studied numerically. The considered parameters affecting the performance of CPOM include the excess enthalpy recovery, gas hourly space velocity (GHSV), number of turns and atomic O/C ratio. The impact of chemical reactions, heat transfer and friction on entropy generation is also analyzed. The results indicate that preheating reactants through waste heat recovery as well as increasing GHSV or number of turns is conducive to enhancing H₂ yield, whereas the maximum H₂ yield develops at O/C = 1.2. A higher H₂ yield is always accompanied by a higher value of entropy generation, and chemical reactions are the main source of entropy generation, especially from steam methane reforming. In contrast, viscous dissipation almost plays no part on entropy generation, compared to heat transfer and chemical reactions. From the analysis of entropy generation, detailed mechanisms of H₂ production from CPOM can be figured out.     

A thermochemical reactor design with better thermal management and improved performance for methane/carbon dioxide dry reforming

A solar thermochemical reactor with better thermal management is proposed to improve the performance for dry reforming of methane. Conical cavity is introduced in the thermochemical reactor to adjust incident solar radiation distribution. Preheating area is adopted to recover sensible heat from gas outlet. Multiphysical model is presented for analyzing the overall performance of the reactor under different inlet flow rates. Also, local ideal reaction temperature required for maximizing local hydrogen production is analyzed according to the reaction kinetics. It is shown that better synergy between real temperature distribution and ideal temperature requirement can be achieved in this new reactor. Compared with conventional reactor, the present reactor exhibits the better performance in terms of reactant conversion, energy storage efficiency and hydrogen yield. Particularly, hydrogen yield is increased by 4.31%–17.12% at inlet flow rates between 6 and 12 L min^?1.     

Steam enhanced carbon dioxide reforming of methane in DBD plasma reactor

Considering the inevitable high energy input to implement the CO₂ reforming of methane under high-temperature operation using conventional catalysis method, the low temperature conversion of CO₂ and methane in the coaxial dielectric barrier discharge (DBD) plasma reactor was investigated in this work. Steam was introduced to enhance the CO₂ reforming of methane with synergetic catalysis effect by cold plasma and catalyst. The experimental results showed that a certain percent of steam could promote the conversion of both CH₄ and CO₂. Meanwhile, the carbon deposition was evidently reduced compared with the dry reforming of methane. With the increase of steam input, the steam reforming occurred predominantly. As a result, the hydrogen volume percentage in the product gases increased. In this way, the products with different H₂/CO ratio could be achieved by changing the mole ratio of CH₄/CO₂/H₂O at the reactor inlet. In particular, when the mole ratio of H₂O/CH₄ increased to almost 3 corresponding to the pure steam reforming process, the conversion of CH₄ reached almost 0.95 and the selectivity to H₂ was almost 0.99 at 773K.     

Potential of Ni supported on clinoptilolite catalysts for carbon dioxide reforming of methane

Carbon dioxide reforming of methane to synthesis gas has been investigated with Ni-supported clinoptilolite catalysts. The catalysts were prepared by using the incipient wetness impregnation method. The catalytic activity of Ni supported on clinoptilolite with varying Ni loadings was determined and the results showed that at 700 °C, 8 wt% Ni/clinoptilolite gave the highest activity. It exhibited not only the highest activity and selectivity but also remarkable stability. Moreover, both the activity and stability of this catalyst were observed to vary with the Zr content, exhibiting a maximum at a composition of 2% Zr. The amount of carbonaceous deposits on the spent catalysts was further investigated by temperature-programmed oxidation (TPO) and thermogravimetric analyzer (TGA) studies.     

ANOVA analysis of an integrated membrane reactor for hydrogen production by methane steam reforming

Steam methane reforming is an endothermic reaction and it used to produce hydrogen and syngas. In this research, a factorial design is developed for an integrated Pd-based membrane reactor, producing hydrogen by methane steam reaction. In literature, no analogous works are present, because a simple sensitivity analysis is carried out without finding significant factors for the process. The reactor is modelled in MATLAB software using the Numaguchi kinetic. The reactor does not use conventional catalysts, but a Ni(10)/CeLaZr catalyst supported on SSiC ceramic foam. In ANOVA analysis, inlet temperature (550 K-815 K), methane flow rate in the feed (0.1 kmol/h-1 kmol/h), hydrogen permeability (1000 m³μmm⁻²hrbar^0.5–3600 m³μmm⁻²hrbar^0.5), the thickness of membrane (0.003 m-0.02 m) are the chosen factors. The analyzed responses are: hydrogen yield, carbon dioxide conversion and methane conversion. Results show that only inlet temperature, methane flow rate, their interaction and the thickens of membrane are significant. Also, the optimal operating conditions are obtained with inlet temperature, methane flow rate, hydrogen permeability and thickness of membrane equal to 550 K, 0.1 kmol/h, 3600 m³μmm⁻²hrbar^0.5 and 0.003 m.     

Hydrogen production through partial oxidation of methane in a new reactor configuration

Performance of the side feeding (SF) air injection in the process of partial oxidation of methane (POM) has been investigated by means of developing a one-dimensional steady-state non-isothermal model. A fixed bed reactor (FBR), a one-side feeding reactor (One-SF), and a membrane reactor (MR) has been compared for the conversion of methane, selectivity of hydrogen and reactor temperature. The results of the model revealed that the One-SF can operate within FBR and MR, and increasing the number of air injections of SF could achieve to the performance of the MR. The performance of the two to five-SF was studied according to the hydrogen selectivity, methane conversion, temperature profile and H₂/CH₄ ratio. It was observed that increasing the number of injections up to the three, increased the selectivity of hydrogen from 0.496 to 0.530 and decreased the outlet temperature from 1269 K to 1078 K. These results lead to creating of a process with controllable operating temperature and enhancing the selectivity of hydrogen. Consequently, decreasing the problems of high operating temperature in FBR and reduction of the process cost compared with MR.     

甲烷快速部分氧化重整试验研究

采用常规浸渍法制备了Rh/α-Al2O3催化剂,建立了甲烷快速部分氧化重整试验体系。通过控制变量法,考察了甲烷快速部分氧化重整反应中反应条件参数(CH4/O2、反应气体预混合温度、空速)变化对反应物的转化率、反应产物及分布的影响。试验结果表明,在试验条件下,CH4的转化率始终大于85%,O2转化率接近100%,CO的选择性为85%左右,H2的选择性为40%～60%。反应过程大致为催化剂入口处的部分氧化反应和下游的水蒸气重整,大部分的CO由部分氧化产生,而H2的产生受水蒸气重整反应的影响较大;随着反应温度的上升,CH4的转化率上升,CO,H2的选择性也上升;随着空速的增大,H2的选择性减小,表明甲烷催化部分氧化反应是一个受传质控制的反应。     

Mathematical simulation of hydrogen production via methanol steam reforming using double-jacketed membrane reactor

The hydrogen production and purification via methanol reforming reaction was studied in a double-jacketed Pd membrane reactor using a 1-D, non-isothermal mathematical model. Both mass and heat transfer behavior were evaluated simultaneously in three parts of the reactor, annular side, permeation tube and the oxidation side. The simulation results exhibited that increasing the volumetric flow rate of hydrogen in permeation side could enhance hydrogen permeation rate across the membrane. The optimum velocity ratio between permeation and annular sides is 10. However, hydrogen removal could lower the temperature in the reformer. The hydrogen production rate increases as temperature increases at a given Damköhler number, but the methanol conversion and hydrogen recovery yield decrease. In addition, the optimum molar ratio of air and methanol was 1.3 with three air inlet temperatures. The performance of a double-jacketed membrane reactor was compared with an autothermal reactor by judging against methanol conversion, hydrogen recovery yield and production rate. Under the same reaction conditions, the double-jacketed reactor can convert more methanol at a given reactor volume than that of an autothermal reactor.     

A comparative study of molybdenum phosphide catalyst for partial oxidation and dry reforming of methane

Molybdenum phosphide (MoP) was firstly used as a catalyst for partial oxidation of methane (POM) and its catalytic performance for POM was compared with that for dry reforming of methane (DRM). It was found that the MoP phase was the dominant active site in POM and DRM reactions, and the activity would gradually decrease when more and more MoP was converted to Mo₂C phase (non-dominant active site) and then rapid deactivation would occur due to bulk oxidation of catalyst. The redox type mechanism over MoP catalyst was vitally important to keep its structure reasonably well during methane reforming reactions. The MoP catalyst revealed a higher catalytic stability in POM than in DRM, attributing to the higher H₂ yield obtained in POM, which can promote and maintain the redox cycle of catalyst.     

Hydrogen production by steam methane reforming in a membrane reactor equipped with a Pd composite membrane deposited on a porous stainless steel

With the aim of producing hydrogen at low cost and with a high conversion efficiency, steam methane reforming (SMR) was carried out under moderate operating conditions in a Pd-based composite membrane reactor packed with a commercial Ru/Al₂O₃ catalyst. A Pd-based composite membrane with a thickness of 4–5 μm was prepared on a tubular stainless steel support (diameter of 12.7 mm, length of 450 mm) using electroless plating (ELP). The Pd-based composite membrane had a hydrogen permeance of 2.4 × 10^?3 mol m^?1 s^?1 Pa^?0.5 and an H₂/N₂ selectivity of 618 at a temperature of 823 K and a pressure difference of 10.1 kPa. The SMR test was conducted at 823 K with a steam-to-carbon ratio of 3.0 and gas hourly space velocity of 1000 h^?1; increasing the pressure difference resulted in enhanced methane conversion, which reached 82% at a pressure difference of 912 kPa. To propose a guideline for membrane design, a process simulation was conducted for conversion enhancement as a function of pressure difference using Aspen HYSYS^®. A stability test for SMR was conducted for ～120 h; the methane conversion, hydrogen production rate, and gas composition were monitored. During the SMR test, the carbon monoxide concentration in the total reformed stream was <1%, indicating that a series of water gas shift reactors was not needed in our membrane reactor system.     

Autothermal reforming of methane for producing high-purity hydrogen in a Pd/Ag membrane reactor

Autothermal reforming of methane includes steam reforming and partial oxidizing methane. Theoretically, the required endothermic heat of steam reforming of methane could be provided by adding oxygen to partially oxidize the methane. Therefore, combining the steam reforming of methane with partial oxidation may help in achieving a heat balance that can obtain better heat efficacy. Membrane reactors offer the possibility of overcoming the equilibrium conversion through selectively removing one of the products from the reaction zone. For instance, only can hydrogen products permeate through a palladium membrane, which shifts the equilibrium toward conversions that are higher than the thermodynamic equilibrium. In this study, autothermal reforming of methane was carried out in a traditional reactor and a Pd/Ag membrane reactor, which were packed with an appropriate amount of commercial Ni/MgO/Al₂O₃ catalyst. A power analyzer was employed to measure the power consumption and to check the autothermicity. The average dense Pd/Ag membrane thickness is 24.3 μm, which was coated on a porous stainless steel tube via the electroless palladium/silver plating procedure. The experimental operating conditions had temperatures that were between 350 °C and 470 °C, pressures that were between 3 atm and 7 atm, and O₂/CH₄ = 0–0.5. The effects of the operating conditions on methane conversion, permeance of hydrogen, H₂/CO, selectivities of CO_x, amount of power supply, and the carbon deposition of the catalyst after the reaction is thoroughly discussed in this paper. The experimental results indicate that an optimum methane conversion of 95%, with a hydrogen production rate of 0.093 mol/m². S, can be obtained from the autothermal reforming of methane at H₂O/CH₄ = 1.3 and O₂/CH₄ near 0.4, at which the reaction does not consume power, and the catalysts are not subject to any carbon deposition.     

Steam reforming of methane over Ni catalyst in micro-channel reactor

A comprehensive study on the catalytic performance of Ni catalyst to implement millisecond steam reforming of methane (SRM) reaction in micro-channel reactors was conducted in this work. A new method to manufacture the metal-ceramics complex substrate as catalyst support was presented, that is, a layer of nano-particles, α-Al₂O₃, was thermally sprayed on a metallic substrate, usually FeCrAlloy. Ni or Rh catalyst was then impregnated on the substrate, forming firm and active catalyst coatings. The fall-off rate of the catalyst can be neglected after the plates experienced the high-temperature SRM reaction, showing the reliability in long-term use and the excellent catalytic performance for SRM reaction in micro-channel reactors. In comparison with the expensive Rh catalyst, Ni also showed wonderful performance to catalyze the SRM reaction in micro-reactors within milliseconds. Using the appropriate reactor design, CH₄ conversion reached above 90% when the residence time was as short as 32 ms for catalyst loading of 6.8 g/m². When the residence time was longer than 100 ms, CH₄ conversion was above 98%. Besides, catalyst deactivation was not detected for 500 h on stream with S/C ratio of 3.0, and for 12 h with S/C of 1.0 as well. Extensive characterizations on these Ni catalyst plates using XRD, SEM, TEM and XPS demonstrated that Ni catalysts prepared in this work did not show any sign of deactivation after being used in the micro-channel system under high-temperature operation.     

Efficient dry reforming of methane with carbon dioxide reaction on Ni@Y2O3 nanofibers anti-carbon deposition catalyst prepared by electrospinning-hydrothermal method

Dry reforming of CH₄ with CO₂ is an effective way to convert these two greenhouse gases into useful industrial feedstock. Here, we designed and developed Ni@Y₂O₃ nanofibers catalyst by pyrolyzing sheet-like Ni₂(CO₃) (OH)₂ grown in situ on the surface of Y₂O₃ nanofibers. Y₂O₃ nanofibers support can not only promote the contact of the reaction gas with the catalyst due to its self-supporting effect, but also improve the ability to capture CO₂ because of its basic oxide properties. Meanwhile, the oxygen exchange between the catalyst and CO₂ could promote the oxidation of carbon deposits, and further improve activity and stability of the catalyst. Besides, the catalyst obtained by low-temperature pyrolysis could maintain the sheet-structure of nickel on the surface of support, which is conducive to improve its catalytic activity, stability, and resistance to carbon deposition. This work has a positive effect on improving the design of catalysts as well as producing industrial chemicals and reducing the environmental pollution.     

Cost‐competitive methane steam reforming in a membrane reactor for H2 production: Technical and economic evaluation with a window of a H2 selectivity

Techno‐economic viability studies of employing a membrane reactor (MR) equipped with H₂ separation membranes for methane steam reforming (MSR) were carried out for H₂ production in Korea using HYSYS®, a well‐known chemical process simulator, including economic analysis based on itemized cost estimation and sensitivity analysis (SA). With the reaction kinetics for MSR reported by Xu and Froment, the effect of a wide range of H₂ selectivity (10‐10,000) on the performance in an MR was investigated in this study. Because of the equilibrium shift owing to the Le Chatelier's principle, great performance of enhancement of methane conversion ( ) and H₂ yield and reaction temperature reduction was observed in an MR compared with a packed‐bed reactor (PBR). A window of a H₂ selectivity from 100 to 300 is proposed as a new criterion for better MR performance of MSR depending on potential applications from in‐depth analysis of and H₂ yield enhancements, a H₂ purity, and temperature reduction. In addition, economic analysis to evaluate the feasibility of an MR technology for MSR was carried out focusing on a levelized cost of H₂ based on itemized cost estimation of capital and operating costs as well as SA. Techno‐economic assessment showed 36.7% cost reduction in an MR compared with a PBR and revealed that this MR technology can be possibly opted for a cost‐competitive H₂ production process for MSR.     

Enhancement effect of heat recovery on hydrogen production from catalytic partial oxidation of methane

The effect of heat recovery on hydrogen production from catalytic partial oxidation of methane (CPOM) and its reaction characteristics in a reactor are investigated using numerical simulations. The reactor is featured by a Swiss-roll structure in which a rhodium (Rh) catalyst bed is embedded at the center of the reactor. By recovering the waste heat from the product gas to preheat the reactants, it is found that the combustion, steam reforming and dry reforming of methane in the catalyst bed are enhanced to a great extent. As a result, the methane conversion and hydrogen yield are improved more than 10%. Considering the operation conditions, a high performance of hydrogen production from CPOM can be achieved if the number of turns in the reactor is increased or the gas hourly space velocity (GHSV) of the reactants in the catalyst bed is lower. However, with the condition of heat recovery, the flow direction of the reactants in the reactor almost plays no part in affecting the performance of CPOM. In summary, the predictions reveal that the reactor with a Swiss-roll structure can be applied for implementing CPOM with high yield of hydrogen.     

Thermodynamic equilibrium analysis of combined carbon dioxide reforming with partial oxidation of methane to syngas

The chemical equilibrium analysis on combined CH₄-reforming with CO₂ and O₂ (combined CORM–POM) has been conducted by total Gibbs energy minimization using Lagrange's undetermined multiplier method. The equilibrium compositions of the combined CORM–POM process were considerably influenced by CH₄:CO₂:O₂ feed ratios and operating temperatures. Methane oxidation reaction occurred predominantly at low temperatures, while the CO₂ conversion was strongly influenced by the O₂/CH₄ feed ratio. The addition of O₂ to the CORM process improved the CH₄ conversion, H₂ and H₂O yields and also the H₂/CO product ratio at the expense of CO₂ conversion and CO yield. Accordingly, the optimal equilibrium conditions for the CH₄:CO₂:O₂ ratio were within the range of 1:0.8:0.2–1:1:0.2 and a minimum requirement temperature of 1000 K.     

Using steam reforming to produce hydrogen with carbon dioxide capture by chemical-looping combustion

In this paper, a novel process for hydrogen production by steam reforming of natural gas with inherent capture of carbon dioxide by chemical-looping combustion is proposed. The process resembles a conventional circulating fluidized bed combustor with reforming taking place in reactor tubes located inside a bubbling fluidized bed. Energy for the endothermic reforming reactions is provided by indirect combustion that takes place in two separate reactors: one for air and one for fuel. Oxygen is transferred between the reactors by a metal oxide. There is no mixing of fuel and air so carbon dioxide for sequestration is easily obtained. Process layout and expected performance are evaluated and a preliminary reactor design is proposed. It is found that the process should be feasible. It is also found that it has potential to achieve better selectivity towards hydrogen than conventional steam reforming plants due to low reactor temperatures and favorable heat-transfer conditions.