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.     

Hydrogen production from methane under the interaction of catalytic partial oxidation,water gas shift reaction and heat recovery

Hydrogen production from the combination of catalytic partial oxidation of methane (CPOM) and water gas shift reaction (WGSR), viz. the two-stage reaction, in a Swiss-roll reactor is investigated numerically. Particular emphasis is placed on the interaction among the reaction of CPOM, the cooling effect due to steam injection and the excess enthalpy recovery with heat recirculation. A rhodium (Rh) catalyst bed sitting at the center of the reactor is used to trigger CPOM, and two different WGSRs, with the aids of a high-temperature (Fe–Cr-based) shift catalyst and a low-temperature (Cu–Zn-based) shift catalyst, are excited. Two important parameters, including the oxygen/methane (O/C) ratio and the steam/methane (S/C) ratio, affecting the efficiencies of methane conversion and hydrogen production are taken into account. The predictions indicate that the O/C ratio of 1.2 provides the best production of H₂ from the two-stage reaction. For a fixed O/C ratio, the H₂ yield is relatively low at a lower S/C ratio, stemming from the lower performance of WGSR, even though the cooling effect of steam is lower. On the contrary, the cooling effect becomes pronounced as the S/C ratio is high to a certain extent and the lessened CPOM leads to a lower H₂ yield. As a result, with the condition of gas hourly space velocity (GHSV) of 10,000 h⁻¹, the optimal operation for hydrogen production in the Swiss-roll reactor is suggested at O/C = 1.2 and S/C = 4–6.     

Enhancement of heat recirculation on the hysteresis effect of catalytic partial oxidation of methane

The hysteresis characteristics of catalytic partial oxidation of methane (CPOM) in a Swiss-roll reactor are predicted numerically by varying Damköhler number. Particular attention is paid to the influences of heat recirculation, gas hourly space velocity (GHSV), and atomic O/C ratio on the hysteresis loop and performance of CPOM. The reactions of methane combustion, steam reforming, and CO₂ or dry reforming are simultaneously considered. The results reveal that preheating reactants through excess enthalpy recovery is conducive to the ignition of CPOM and extending its extinction limit, so the ignition and extinction Damköhler numbers are lowered. The analysis also suggests that steam reforming is more sensitive to the heat recovery than methane combustion and dry reforming. An increase in GHSV reduces the residence time of reactants in the catalyst bed, thereby enlarging the ignition and extinction Damköhler numbers of CPOM. A higher O/C ratio facilitates the ignition of CPOM, stemming from more oxygen supplied, but the ratio should be controlled below 1.2. From the hysteresis phenomena, hydrogen can be produced from methane at a lower Damköhler number to save more energy for performing CPOM.     

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.     

Hysteresis loops of methane catalytic partial oxidation for hydrogen production under the effects of varied Reynolds number and Damköhler number

Hysteresis loops of catalytic partial oxidation of methane (CPOM) for hydrogen production under the effects of varied Reynolds number and Damköhler number are investigated numerically in this study. The physical phenomena are predicted using the indirect mechanism, which consists of the total oxidation (or combustion), steam reforming and CO₂ reforming of methane in a catalyst bed. Numerical results reveal that, when the Damköhler number is relatively low, a hysteresis loop of CPOM from varying Reynolds number develops. Increasing the Damköhler number leads to the loop shifting toward the regime of high Reynolds number. However, once the Damköhler number is large to a certain extent, the chemical reactions are always exhibited for the Reynolds number less than 2000. A closed loop is thus not observed. Alternatively, for a given Reynolds number, an ignited Damköhler number and an extinguished Damköhler number can be obtained. Accordingly, three different regions in the plot of Damköhler number versus Reynolds number are identified. Physically, when the role played by Damköhler number on CPOM is much more important than by the Reynolds number (Region I), the thermal effect governs the chemical reactions. In contrast, if the Reynolds number plays a key role in determining the CPOM (Region III), the chemically frozen flow prevails over the catalyst bed. When the residence times of the total oxidation and convection in the catalyst bed are in an equivalent state (Region II), CPOM is characterized by a dual-solution, rendering the hysteresis loops. From the distributions of ignited and extinguished Damköhler numbers, the catalytic reactor and operation of partial oxidation of methane and other fuels can be designed accordingly.     

Hydrogen production by coupled catalytic partial oxidation and steam methane reforming at elevated pressure and temperature

Hydrogen production by coupled catalytic partial oxidation (CPO) and steam methane reforming of methane (OSMR) at industrial conditions (high temperatures and pressures) have been studied over supported 1 wt.% NiB catalysts. Mixture of air/CH₄/H₂O was applied as the feed. The effects of O₂:CH₄ ratio, H₂O:CH₄ ratio and the gas hourly space velocity (GHSV) on oxy-steam reforming (OSRM) were also studied. Results indicate that CH₄ conversion increases significantly with increasing O₂:CH₄ or H₂O:CH₄ ratio. However, the hydrogen mole fraction goes through a maximum, depending on reaction conditions, e.g., pressure, temperature and the feed gases ratios. Carbon deposition on the catalysts has been greatly decreased after steam addition. The supported 1 wt.% NiB catalysts exhibit high stability with 85% methane conversion at 15 bar and 800 °C during 70 h time-on-stream reaction (CH₄:O₂:H₂O:N₂ = 1:0.5:1:1.887). The thermal efficiency was increased from 35.8% by CPO (without steam) to 55.6%. The presented data would be useful references for further design of enlarged scale hydrogen production system.     

Hysteresis and reaction characterization of methane catalytic partial oxidation on rhodium catalyst

Hysteresis effects and reaction characteristics of methane catalytic partial oxidation (CPO) in a fixed-bed reactor are numerically simulated. The reactions are modeled based on the experimental measurements of methane CPO with a rhodium (Rh) catalyst. Three C/O ratios of 0.6, 1.0 and 1.4 are considered in the study. When the Reynolds number is 200, the predictions indicate that the methane CPO is always triggered at around the inlet temperature of 550 K, regardless of what the C/O ratio is. It is of interest that if the inlet temperature is decreased after the methane CPO develops at higher inlet temperatures, the reversed path of methane conversion is different from the original path at lower inlet temperatures. The hysteresis effect of the methane CPO is thus observed. The hysteresis behavior implies that a higher yield of syngas or hydrogen can be achieved by controlling the reaction process. Decreasing the C/O ratio intensifies the methane CPO so that the hysteresis effect is more pronounced, and vice versa. An increase in Reynolds number delays the excitation temperature of methane CPO and lessens the hysteresis effect of methane conversion due to the growth of fluid inertial force. However, the hysteresis effect of the maximum temperature in the catalyst bed increases as a result of more methane consumption.     

Thermodynamic analysis of hydrogen production from methane via autothermal reforming and partial oxidation followed by water gas shift reaction

Reaction characteristics of hydrogen production from a one-stage reaction and a two-stage reaction are studied and compared with each other in the present study, by means of thermodynamic analyses. In the one-stage reaction, the autothermal reforming (ATR) of methane is considered. In the two-stage reaction, it is featured by the partial oxidation of methane (POM) followed by a water gas shift reaction (WGSR) where the temperatures of POM and WGSR are individually controlled. The results indicate that the reaction temperature of ATR plays an important role in determining H₂ yield. Meanwhile, the conditions of higher steam/methane (S/C) ratio and lower oxygen/methane (O/C) ratio in association with a higher reaction temperature have a trend to increase H₂ yield. When O/C ≤ 0.125, the coking behavior may be exhibited. In regard to the two-stage reaction, it is found that the methane conversion is always high in POM, regardless of what the reaction temperature is. When the O/C ratio is smaller than 0.5, H₂ is generated from the partial oxidation and thermal decomposition of methane, causing solid carbon deposition. Following the performance of WGSR, it suggests that the H₂ yield of the two-stage reaction is significantly affected by the reaction temperature of WGSR. This reflects that the temperature of WGSR is the key factor in producing H₂. When methane, oxygen and steam are in the stoichiometric ratio (i.e. 1:0.5:1), the maximum H₂ yield from ATR is 2.25 which occurs at 800 °C. In contrast, the maximum H₂ yield of the two-stage reaction is 2.89 with the WGSR temperature of 200 °C. Accordingly, it reveals that the two-stage reaction is a recommended fuel processing method for hydrogen production because of its higher H₂ yield and flexible operation.     

Hydrogen production by catalytic partial oxidation of methane and propane on Ni and Pt catalysts

In recent years the catalytic partial oxidation has been taken into consideration as a suitable process for hydrogen production, because of its exothermic nature which makes the process less energy and capital cost intensive with respect to steam reforming. In this paper the behaviour of three different catalyst typologies, two based on Ni–_Al2O3${\mathrm{Al}}_2{\mathrm{O}}_3$ (different in active phase composition) and one constituted by Pt supported on _CeO2${\mathrm{CeO}}_2$, is studied for partial oxidation of propane (as representative of liquefied petroleum gas). For comparison the same catalysts have been tested also in methane partial oxidation.     

Effect of sulphur during the catalytic partial oxidation of ethane over Rh and Pt honeycomb catalysts

The impact of sulphur addition (2–58 ppm) during the catalytic partial oxidation (CPO) of ethane was investigated on Rh- and Pt-based honeycomb catalysts tested under self-sustained high temperature conditions. Both steady state and transient operation of the CPO reactor were investigated particularly with regards to poisoning/regeneration cycles. A detailed analysis of products distribution in the effluent and a heat balance of the CPO reactor demonstrates that sulphur reversibly adsorbed on Rh selectively inhibits the ethane hydrogenolysis and, to a lower extent, steam reforming reaction. A further, simultaneous adverse effect of S on the kinetics of the reverse water gas shift reaction on Rh catalyst operating at temperatures < 750 °C can cause an unexpected increase in the H₂ yield above its equilibrium value for low concentrations of the poison. Pt catalyst is less active for those reactions but in turn is more S-tolerant.     

Assessment of CO2 capture options from various points in steam methane reforming for hydrogen production

Steam methane reforming (SMR) is currently the main hydrogen production process in industry, but it has high emissions of CO₂, at almost 7 kg CO₂/kg H₂ on average, and is responsible for about 3% of global industrial sector CO₂ emissions. Here, the results are reported of an investigation of the effect of steam-to-carbon ratio (S/C) on CO₂ capture criteria from various locations in the process, i.e. synthesis gas stream (location 1), pressure swing adsorber (PSA) tail gas (location 2), and furnace flue gases (location 3). The CO₂ capture criteria considered in this study are CO₂ partial pressure, CO₂ concentration, and CO₂ mass ratio compared to the final exhaust stream, which is furnace flue gases. The CO₂ capture number (N_cc) is proposed as measure of capture favourability, defined as the product of the three above capture criteria. A weighting of unity is used for each criterion. The best S/C ratio, in terms of providing better capture option, is determined. CO₂ removal from synthesis gas after the shift unit is found to be the best location for CO₂ capture due to its high partial pressure of CO₂. However, furnace flue gases, containing almost 50% of the CO₂ in produced in the process, are of great significance environmentally. Consequently, the effects of oxygen enrichment of the furnace feed are investigated, and it is found that this measure improves the CO₂ capture conditions for lower S/C ratios. Consequently, for an S/C ratio of 2.5, CO₂ capture from a flue gas stream is competitive with two other locations provided higher weighting factors are considered for the full presence of CO₂ in the flue gases stream. Considering carbon removal from flue gases, the ratio of hydrogen production rate and N_cc increases with rising reformer temperature.     

Simulation of a fuel reforming system based on catalytic partial oxidation

Catalytic partial oxidation (CPO) has potential for producing hydrogen that can be fed to a fuel cell for portable power generation. In order to be used for this purpose, catalytic partial oxidation must be combined with other processes, such as water-gas shift and preferential oxidation, to produce hydrogen with minimal carbon monoxide. This paper evaluates the use of catalytic partial oxidation in an integrated system for conversion of a military logistic fuel, JP-8, to high-purity hydrogen. A fuel processing system using CPO as the first processing step is simulated to understand the trade-offs involved in using CPO. The effects of water flow rate, CPO reactor temperature, carbon to oxygen ratio in the CPO reactor, temperature of preferential oxidation, oxygen to carbon ratio in the preferential oxidation reactor, and temperature for the water-gas shift reaction are evaluated. The possibility of recycling water from the fuel cell for use in fuel processing is evaluated. Finally, heat integration options are explored. A process efficiency, defined as the ratio of the lower heating value of hydrogen to that of JP-8, of around 53% is possible with a carbon to oxygen ratio of 0.7. Higher efficiencies are possible (up to 71%) when higher C/O ratios are used, provided that olefin production can be minimized in the CPO reactor.     

Calcium silicate-based catalytic filters for partial oxidation of methane and biogas mixtures: Preliminary results

Development and testing of catalytic filters for partial oxidation of methane to increase hydrogen production in a biomass gasification process constitute the subject of the present study. Nickel, iron and lanthanum were coated on calcium silicate filters via co-impregnation technique, and catalytic filters were characterized by ICP-MS, XPS, XRD, TEM, TGA, TPR and BET techniques. The influences of varying reaction temperature and addition of Fe or La to Ni-based catalytic filters on methane conversion, and hydrogen selectivity have been investigated in view of preliminary results obtained from reactions with 6% methane-nitrogen mixture, and catalytic filters were tested with model biogas mixtures at optimum reaction temperature of each filter which were 750 °C or 850 °C. Approximately 93% methane conversion was observed with nearly 6% methane-nitrogen mixture, and 97.5% methane conversion was obtained with model biogas containing CH₄ which is 6%, CO₂, CO, and N₂ at 750 °C. These results indicate that calcium silicate provides a suitable base material for catalytic filters for partial oxidation of methane and biogas containing methane.     

Optimization of a counter-flow microchannel reactor using hydrogen assisted catalytic combustion for steam reforming of methane

The objective of this study is to optimize a microchannel reactor using hydrogen assisted catalytic combustion for steam reforming of methane. Hydrogen assisted catalytic combustion does not require preheating because the catalytic combustion of hydrogen occurs at room temperature. After start-up by hydrogen catalytic combustion, fuels of hydrogen and methane were changed to methane. The geometric configuration of the counter-flow reactor was optimized by the simulation model under steady state condition. The hydrogen flow rate in the counter-flow reactor was also optimized by transient simulations using the response surface methodology. As a result, the counter-flow reactor showed extremely short start-up time because of the optimized configuration and the optimized hydrogen flow rate. Hot spots were avoided because of the hydrogen shut-off after start-up. The operating characteristics of the counter-flow reactor were compared with those of the co-flow reactor.     

Modeling of fractal heat conduction of semi-coke bed in waste heat recovery steam generator for hydrogen production

With the steam obtained from the waste heat of high temperature semi-coke, the hydrogen production through gasification method is considered more commercial. In order to improve the efficiency of waste heat recovery, the fractional model for heat conduction of semi-coke bed in waste heat recovery process was established. The non-destructive CT was employed to obtain the inner morphology of semi-coke bed and the image binarization processing was used to segment the CT image. With the MATLAB program, the box-counting method was used to calculate the fractal dimension of semi-coke bed. The fractional model for heat conduction of semi-coke bed was established by the fractal theory. The results showed that, the CT image and bit binary image of semi-coke bed can really reflect the inner morphology of semi-coke bed, and the inner morphology of semi-coke bed can be regarded as a fractal medium. The fractal dimension of semi-coke bed is 1.7537, which is very close to golden mean, 1.618, this could be the optimal structure for the heat conduction of semi-coke bed under the condition of natural accumulation. The one-dimensional heat conduction fractional equation of semi-coke bed was established and it can be accurately solved by fractal complex transformation and traveling wave transformation.     

Partial oxidation of methane on neodymium and lanthanium chromate based perovskites for hydrogen production

Perovskite-type mixed oxides LaCrO₃ and Nd_0.95CrO₃ were synthesized by the polymerization complex method. The perovskites were characterized by different techniques aiming to evaluate the influence of the non-stoichiometry and the nature of site A on the catalytic properties for the POM reaction. The non-stoichiometry and A sites did not affect the methane conversion, but the selectivity. The methane conversion with the neodymium catalyst Nd_0.95CrO₃ (N95) was 34%, and of the mixed La_0.95CrO₃ (L95) catalyst 38%, under these conditions. The rate of the Nd_0.95CrO₃ (N95) perovskite was equal to 3.50 mol.g⁻¹.h⁻¹ at 700 °C, which suggests higher activity compared to cobaltate perovskites. Although the hydrogen selectivity was similar the selectivity to CO and CO₂ were different. Catalysts did not suffer structure changes during the POM reaction and negligible deactivation.     

Numerical study of heat transfer characteristics of semi-coke and steam in waste heat recovery steam generator for hydrogen production

With the steam obtained from the waste heat of high temperature semi-coke, the hydrogen production through gasification method is considered more commercially. The heat transfer of semi-coke bed and steam was investigated using an unsteady convection heat transfer three-dimensional model of semi-coke. The effects of particle size, steam flow and particle bed thickness on heat transfer characteristics were considered. The particle temperature calculated by three-dimensional model was in good agreement with the corresponding particle temperature of experiment. The heat transfer characteristics of single particle, the particle temperature, the amount of heat recovery and the heat flux were investigated. The results show that, in the first 10 min of the heat transfer of semi-coke bed and steam, the bottom particle temperature decreases rapidly, but the top particle temperature is almost unchanged. The heat transfer rate evolution of the single particle in different positions is revealed. The heat transfer rate evolution of the bottom particle is different from that of the middle particle and top particle, and the heat transfer rate evolution of middle particle is similar to that of the top particle. The particle size, the steam flow and the particle bed thickness have great influence on the heat transfer mechanism of semi-coke and steam, and the 7.5 kg/h is considered to be the best steam flow for heat recovery. The intrinsic heat transfer mechanism between semi-coke bed and steam was revealed.     

Numerical investigation of hydrogen production via autothermal reforming of steam and methane over Ni/Al2O3 and Pt/Al2O3 patterned catalytic layers

In this study a numerical analysis of hydrogen production via an autothermal reforming reactor is presented. The endothermic reaction of steam methane reforming and the exothermic combustion of methane were activated with patterned Ni/Al₂O₃ catalytic layer and patterned Pt/Al₂O₃ catalytic layer, respectively. Aiming to achieve a more compacted process, a novel design of a reactor was proposed in which the reforming and the combustion catalysts were modeled as patterned thin layers. This configuration is analyzed and compared with two configurations. In the first configuration, the catalysts are modeled as continuous thin layers in parallel, while, in the second configuration the catalysts are modeled as continuous thin layers in series (conventional catalytic autothermal reactor). The results show that the pattern of the catalyst layers improves slightly the hydrogen yield, i.e. 3.6%. Furthermore, for the same concentration of hydrogen produced, the activated zone length can be decreased by 38% and 15% compared to the conventional catalytic autothermal reforming and the configuration where the catalysts are fitted in parallel, respectively. Besides, the oxygen consumption is lowered by 5%. The decrement of the catalyst amount and the oxygen feedstock in the novel studied design lead to lower costs and compact process.     

Characteristics of combined carbon dioxide reforming with partial oxidation of methane to produce hydrogen in the membrane reactor

Thermodynamic equilibrium constant method and mathematical model are used to analyze the investigating effects of temperature, α[oxygen‐methane molar ratio] and β [carbon dioxide‐methane molar ratio] on characteristics of oxidative CO₂ reforming of methane reaction over Ni/Al₂O₃ catalysts to produce hydrogen in the membrane reactor. While keeping temperature at 1100 K, the membrane reactor is no longer useful to separate hydrogen when α > 0.6 for hydrogen in reaction side is no longer to permeate side. When increasing β, the methane conversion goes up firstly until the β is 1.3, which is higher than the inflection point at 1.1 in the model prediction. The hydrogen yield peaks at β = 0.5 in permeate side. Increasing the temperature or reducing the β will cause the molar ratio of H₂/CO increase. However, changing α has no significant effect on adjusting the molar ratio of H₂/CO. By establishing equilibrium reaction model, the system performance can be accurately predicted. Copyright © 2016 John Wiley & Sons, Ltd.