A novel integrated thermally coupled configuration for methane-steam reforming and hydrogenation of nitrobenzene to aniline

In this work, a novel thermally coupled reactor containing the steam reforming process in the endothermic side and the hydrogenation of nitrobenzene to aniline in the exothermic side has been investigated. In this novel configuration, the conventional steam reforming process has been substituted by the recuperative coupled reactors which contain the steam reforming reactions in the tube side, and the hydrogenation reaction in the shell side. The co-current mode is investigated and the simulation results are compared with corresponding predictions for an industrial fixed-bed steam reformer reactor operated at the same feed conditions. The results show that although synthesis gas productivity is the same as conventional steam reformer reactor, but aniline is also produced as an additional valuable product. Also it does not need to burn at the furnace of steam reformer. The performance of the reactor is numerically investigated for different inlet temperature and molar flow rate of exothermic side. The reactor performance is analyzed based on methane conversion, hydrogen yield and nitrobenzene conversion. The results show that exothermic feed temperature of 1270 K can produce synthesis gas with 26% methane conversion (the same as conventional) and nitrobenzene conversion in the outlet of the reactor is improved to 100%. This new configuration eliminates huge fired furnace with high energy consumption in steam reforming process.     

Multi-objective optimization of aniline and hydrogen production in a directly coupled membrane reactor

A numerical study of aniline production by hydrogenation of nitrobenzene (NBH) and hydrogen production by steam methane reforming (SMR) in a directly coupled membrane reactor is developed. This membrane reactor was proposed aiming to decarbonize heating in SMR and to favor the recovery of all products. Aniline recovery is improved in this reactor as water, a byproduct in NBH, is consumed in SMR. The simulation is performed using a heterogeneous-one dimensional model (Dusty gas model) and results are compared against the homogeneous model. The operating conditions of the reactor were selected using a multi-objective optimization method, genetic algorithms. The aims of the optimization were: methane conversion maximization, minimum membrane area, minimum reactor size, hydrogen yield maximization, nitrobenzene conversion maximization and the maximization of hydrogen recovery. This process was able to achieve complete conversion of methane and nitrobenzene. The hydrogen yield achieved can be as high as the maximum (～4). 35% of this hydrogen was used as a reactant for aniline production. 99% of the unreacted hydrogen was recovered and purified. As the steam flow was minimized, aniline was obtained with a molar composition (70%), 2.1 times higher than that obtained in a conventional process for aniline production (33%). CO₂ was obtained with a purity of 97%, hence, CO₂ carbon capture and storage techniques were also favored. In addition, the energy requirements of heating of feedstock, reaction and recovery system of this novel process was 2.7 times lower than that of conventional processes carried out independently.     

Simultaneous production of two types of synthesis gas by steam and tri‐reforming of methane using an integrated thermally coupled reactor: mathematical modeling

In this work, tri‐reforming and steam reforming processes have been coupled thermally together in a reactor for production of two types of synthesis gases. A multitubular reactor with 184 two‐concentric‐tubes has been proposed for coupling reactions of tri‐reforming and steam reforming of methane. Tri‐reforming reactions occur in outer tube side of the two‐concentric‐tube reactor and generate the needed energy for inner tube side, where steam reforming process is taking place. The cocurrent mode is investigated, and the simulation results of steam reforming side of the reactor are compared with corresponding predictions for thermally coupled steam reformer and also conventional fixed‐bed steam reformer reactor operated at the same feed conditions. This reactor produces two types of syngas with different H₂/CO ratios. Results revealed that H₂/CO ratio at the output of steam and tri‐reforming sides reached to 1.1 and 9.2, respectively. In this configuration, steam reforming reaction is proceeded by excess generated heat from tri‐reforming reaction instead of huge fired‐furnace in conventional steam reformer. Elimination of a low performance fired‐furnace and replacing it with a high performance reactor causes a reduction in full consumption with production of a new type of synthesis gas. The reactor performance is analyzed on the basis of methane conversion and hydrogen yield in both sides and is investigated numerically for various inlet temperature and molar flow rate of tri‐reforming side. A mathematical heterogeneous model is used to simulate both sides of the reactor. The optimum operating parameters for tri‐reforming side in thermally coupled tri‐reformer and steam reformer reactor are methane feed rate and temperature equal to 9264.4 kmol h^?1 and 1100 K, respectively. By increasing the feed flow rate of tri‐reforming side from 28,120 to 140,600 kmol h^?1, methane conversion and H₂ yield at the output of steam reforming side enhanced about 63.4% and 55.2%, respectively. Also by increasing the inlet temperature of tri‐reforming side from 900 to 1300 K, CH₄ conversion and H₂ yield at the output of steam reforming side enhanced about 82.5% and 71.5%, respectively. The results showed that methane conversion at the output of steam and tri‐reforming sides reached to 26.5% and 94%, respectively with the feed temperature of 1100 K of tri‐reforming side. Copyright © 2013 John Wiley & Sons, Ltd.     

Demonstration of a scaled-down autothermal membrane methane reformer for hydrogen generation

A novel concept for hydrogen generation by methane steam reforming in a thermally coupled catalytic fixed bed membrane reformer is experimentally demonstrated. The reactor, built from three concentric compartments, indirectly couples the endothermic methane steam reforming with the exothermic methane oxidation, while hydrogen is separated by a permselective Pd membrane. The study focuses on the determination of the key operation parameters and understanding their influence on the reactor performance. It has been shown that the reactor performance is mainly defined by the dimensionless ratio of the methane steam reforming feed flow rate to the hydrogen maximal membrane flow rate and by the ratio of the oxidation and steam reforming methane feed flow rates.     

Mathematical modeling of a multi-stage naphtha reforming process using novel thermally coupled recuperative reactors to enhance aromatic production

In this study, a novel thermally coupled reactor containing the naphtha reforming process in the endothermic side and the hydrogenation of nitrobenzene to aniline in the exothermic side has been investigated. Considering the higher thermal efficiency as well as the smaller size of the reactor, utilizing the recuperative coupled reactor is given priority. In this novel configuration, the first and the second reactor of the conventional naphtha reforming process have been substituted by the recuperative coupled reactors which contain the naphtha reforming reactions in the shell side, and the hydrogenation reaction in the tube side. The achieved results of this simulation have been compared with the results of the conventional fixed-bed naphtha reforming reactors. Acceptable enhancement can be noticed in the performance of the reactors. The production rate of the high octane aromatics and the consumption rate of the paraffins have improved 17% and 72%, respectively. The conversion of the nitrobenzene is acceptable and the effect of the number of the tubes also has been taken into account. However, the performance of the new configuration needs to be tested experimentally over a range of parameters under practical operating conditions.     

Simulation of a porous ceramic membrane reactor for hydrogen production

A systematic simulation study was performed to investigate the performance of a porous ceramic membrane reactor for hydrogen production by means of methane steam reforming. The results show that the methane conversions much higher than the corresponding equilibrium values can be achieved in the membrane reactor due to the selective removal of products from the reaction zone. The comparison of isothermal and non-isothermal model predictions was made. It was found that the isothermal assumption overestimates the reactor performance and the deviation of calculation results between the two models is subject to the operating conditions. The effects of various process parameters such as the reaction temperature, the reaction side pressure, the feed flow rate and the steam to methane molar feed ratio as well as the sweep gas flow rate and the operation modes, on the behavior of membrane reactor were analyzed and discussed.     

A comparison of two different flow types on performance of a thermally coupled recuperative reactor containing naphtha reforming process and hydrogenation of nitrobenzene

Refineries have been looking for proper ways of improving reformer performance by enhancing the octane number of the product via increasing the aromatics’ compounds. To reach this goal, the endothermic catalytic naphtha reforming is coupled with the exothermic hydrogenation of nitrobenzene to aniline in a multifunctional heat exchanger reactor through the process intensification concept. Considering the higher thermal efficiency as well as the smaller size of the coupled reactor, utilizing this reactor is given priority. In this novel configuration, the first and the second reactor of the conventional naphtha reforming process are exchanged with the coupled reactors contain the endothermic naphtha reforming in the shell side and the hydrogenation reaction in the tube side. Both co-current and counter-current modes of flow are examined during the operation considering various studies in literature which show the superiority of co-current flow compared with the counter-current flow. The result of current study is compared with the corresponding results for conventional tubular reactor (CTR). The results show higher aromatic production as much as 18.73% and 16.48% in the co-current and counter-current mode, respectively. Hydrogen molar flow rate increases about 5 kmol/h by using counter-current flow regime, compared with the CTR.     

Modeling and simulation of circulating fast fluidized bed reactors and circulating fast fluidized bed membrane reactors for production of hydrogen by oxidative reforming of methane

Modeling and simulation of circulating fast fluidized bed reactors (CFFBR) and circulating fast fluidized bed membrane reactors (CFFBMR) for hydrogen production by oxidative reforming of methane are presented in this paper. The results show that the CFFBR suffers from serious problems of hot spot temperatures. The combined effect of the oxygen distribution and the hydrogen membrane in the CFFBMR eliminates the hot spot temperatures and the danger of the reactor thermal runaway and mitigates nicely the temperature along the length of the CFFBMR. The investigation shows that the oxidative reforming of methane in the CFFBMR with oxygen distribution is cost-effective and inexpensive alternative route to the conventional steam reforming of methane processes due to the in situ heat integration of exothermic and endothermic reactions. The key role of the design parameters on the performance of the reactors are recognized through sensitivity analysis. The simulation results indicate that almost complete conversion of methane (99.99%), high exit hydrogen yield of 3.00 and low exit temperature of 569.8 °C are obtained by proper selection of design parameters of the CFFBMR with oxygen distribution. This achievement occurs at low feed temperature of 350.0 °C, which does not have destructive effects on the catalyst, reactor and membrane.     

Simulation of steam reforming of biogas in an industrial reformer for hydrogen production

The paper aims to investigate the steam reforming of biogas in an industrial-scale reformer for hydrogen production. A non-isothermal one dimensional reactor model has been constituted by using mass, momentum and energy balances. The model equations have been solved using MATLAB software. The developed model has been validated with the available modeling studies on industrial steam reforming of methane as well as with the those on lab-scale steam reforming of biogas. It demonstrates excellent agreement with them. Effect of change in biogas compositions on the performance of industrial steam reformer has been investigated in terms of methane conversion, yields of hydrogen and carbon monoxide, product gas compositions, reactor temperature and total pressure. For this, compositions of biogas (CH₄/CO₂ = 40/60 to 80/20), S/C ratio, reformer feed temperature and heat flux have been varied. Preferable feed conditions to the reformer are total molar feed rate of 21 kmol/h, steam to methane ratio of 4.0, temperature of 973 K and pressure of 25 bar. Under these conditions, industrial reformer fed with biogas, provides methane conversion (93.08–85.65%) and hydrogen yield (1.02–2.28), that are close to thermodynamic equilibrium condition.     

Thermodynamic analysis of high‐temperature helium heated fuel reforming for hydrogen production

In order to take full advantage of the heat from high temperature gas cooled reactor, thermodynamic analysis of high‐temperature helium heated methane, ethanol and methanol steam reforming for hydrogen production based on the Gibbs principle of minimum free energy has been carried out using the software of Aspen Plus. Effects of the reaction temperature, pressure and water/carbon molar ratio on the process are evaluated. Results show that the effect of the pressure on methane reforming is small when the reaction temperature is over 900 °C. Methane/CO conversion and hydrogen production rate increase with the water/carbon molar ratio. However the thermal efficiency increases first to the maximum value of 61% and then decreases gradually. As to ethanol and methanol steam reforming, thermal efficiency is higher at lower reaction pressures. With an increase in water–carbon molar ratio, hydrogen production rate increases, but thermal efficiency decreases. Both of them increase with the reaction temperature first to the highest values and then decrease slowly. At optimum operation conditions, the conversion of both ethanol and methanol approaches 100%. For the ethanol and methanol reforming, their highest hydrogen production rate reaches, respectively, 88.69% and 99.39%, and their highest thermal efficiency approaches, respectively, 58.58% and 89.17%. With the gradient utilization of the high temperature helium heat, the overall heat efficiency of the system can reach 70.85% which is the highest in all existing system designs. Copyright © 2014 John Wiley & Sons, Ltd.     

A two-dimensional mathematical model for the catalytic steam reforming of methane in both conventional fixed-bed and fixed-bed membrane reactors for the Production of hydrogen

A modelling and simulation study of catalytic steam reforming of methane is presented in this paper. A two-dimensional pseudo-heterogeneous model is developed to simulate a conventional fixed-bed reactor (FBR) as well as a fixed-bed membrane reactor (FBMR) with sweep gas added in both co-current modes for the two reactor configurations. The developed model is based on mass and energy balance equations for the catalyst phase and the gas phase in both FBR and FBMR reactors. Firstly, a study is done for describing that the temperature profiles of gaseous and solid phases reach to stable state as well as the component distributions in the two FBR and FBMR reactors. The model covers the aspect of the partial pressure of hydrogen in the membrane reactor with the permeation of hydrogen across a Pd-based membrane. The conversion of methane is significantly enhanced by the partial removal of hydrogen as from the shell side as a result of diffusion through the Pd-based membrane. Simulation results demonstrated that methane conversion of 97.21% can be achieved in FBR at operating temperature of 1250 K relative to methane conversion of 99.79% to 923 K in FBMR. The yield of hydrogen achieved to level from 2.154 in FBR at operating temperature of 1250 K while the yield of hydrogen reached to level from 3.731 with a thickness from 1.7 μm in FBMR reactor.     

Efficient operation of autothermal microchannel reactors for the production of hydrogen by steam methane reforming

Efficient conversion of methane to hydrogen has emerged as a significant challenge to realizing fuel cell-based energy systems. Autothermal microchannel reactors, coupling of exothermic and endothermic reactions in parallel channels, have become one of the most promising technologies in the field of hydrogen production. Such reactors were utilized as an intensified design for conducting the endothermic steam methane reforming reaction. The energy required by the endothermic process is supplied directly through the separating plates of the reactor structure from the exothermic process occurring on the opposing side. Optimal design problems associated with transport phenomena in such an autothermal system were analyzed. Various methods for designing and operating autothermal reactors employed in steam methane reforming were discussed. Computational fluid dynamics simulations were performed to identify the underlying principles of process intensification, and to delineate several design and operational features of the intensified reforming process. The results indicated that the autothermal reactor is preferable to be thermally conductive to ensure its structural integrity and maximum operating regime. However, the thermal properties of the reactor structure are not essential due to efficient heat transfer existing between endothermic and exothermic process streams. A reactor design which minimizes the mass transfer resistance is highly required, and the channel dimension is of critical importance. Furthermore, the challenges presented by the efficient operation of the autothermal system were identified, along with demonstrating the implementation of transport management in order to improve overall reactor performance and to mitigate extreme temperature excursions.     

Optimal conditions for hydrogen production from coupling of dimethyl ether and benzene synthesis

Coupling energy intensive endothermic reaction systems with suitable exothermic reactions followed by hydrogen permeation through the Pd/Ag membrane improves the thermal efficiency of processes, achieving the autothermality within the reactor, reduces the size of reactors, produces the pure hydrogen, and achieving a multiple reactants multiple products configuration. This paper focuses on optimization of hydrogen, dimethyl ether (DME) and benzene production in a membrane thermally coupled reactor. A steady-state heterogeneous mathematical model that is composed of three sides is developed to predict the performance of this novel configuration reactor. The catalytic methanol dehydration to DME takes place in the exothermic side that supplies the necessary heat for the catalytic dehydrogenation of cyclohexane to benzene reaction in the endothermic side. Selective permeation of hydrogen through the Pd/Ag membrane is achieved by co-current flow of sweep gas through the permeation side. This novel configuration can decrease the temperature of methanol dehydration reaction in the second half of the reactor and shift the thermodynamic equilibrium. The differential evolution (DE), an exceptionally simple evolution strategy, is applied to optimize membrane thermally recuperative coupled reactor considering the summation of methanol and cyclohexane conversions and dimensionless hydrogen recovery yield as the main objectives. The simulation results have been shown that there are optimum values of initial molar flow rate of exothermic and endothermic sides and inlet temperature of exothermic, endothermic and permeation sides to maximize the objective function. The optimization method has enhanced the methanol conversion by 2.76%. The optimization results are compared with corresponding predictions for a conventional (industrial) methanol dehydration adiabatic reactor operated at the same feed conditions. The results suggest that coupling of these reactions could be feasible and beneficial. An experimental proof-of-concept is needed to establish the validity and safe operation of the novel reactor.     

Production of hydrogen and methanol enhancement via a novel optimized thermally coupled two‐membrane reactor

This study focuses on optimum operating conditions for thermally coupled two‐membrane reactor (TCTMR) to maximize ultrapure hydrogen and methanol production as alternative environmentally friendly fuels. Hydrogen is used in chemical and petrochemical industries especially applicable in fuel cell technologies, with zero CO₂ emission. In the proposed configuration, methanol synthesis is carried out in the exothermic side by hydroxy sodalite membrane and supplies the necessary heat for the endothermic side. Dehydrogenation of cyclohexane is carried out in the endothermic side with hydrogen‐permselective Pd/Ag membrane wall. A one‐dimensional, steady‐state heterogeneous model and the differential evolution method, as a strong and powerful optimization method, are applied to simulate and optimize the proposed reactor configuration. The simulation results have been shown that there are optimal values of the initial molar flow rate of endothermic, outer and the inner permeation stream, inlet temperature of exothermic, endothermic, outer and inner permeation sides and inlet pressure of inner permeation side to maximize the objective function. The optimization results show 5.87 and 10.51% increase in the methanol production in optimized TCTMR compared with TCTMR and a conventional reactor, respectively. Moreover, this novel configuration with optimal conditions raises the hydrogen production rate about 1.1847 ton/day. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Methanol steam reforming reaction in a Pd–Ag membrane reactor for CO-free hydrogen production

A dense tubular Pd–Ag membrane reactor was used to carry out the methanol steam reforming reaction for producing a CO-free hydrogen stream. A Cu/Zn/Mg-based catalyst was packed in the lumen side of the membrane reactor and the experimental tests were performed at a reaction temperature of 300 °C and at a H₂O/methanol feed molar ratio of 3/1. The effects of the different flow configurations, as well as the sweep factor and the reaction pressure were analysed. Experimental results in terms of CO-free hydrogen recovery, hydrogen yield, CO-free hydrogen yield and hydrogen selectivity are presented. Moreover, a comparison between the performances of the membrane reactor and a traditional reactor working at the same operative conditions is proposed and discussed.     

Performance analysis of a membrane‐based reformer‐combustor reactor for hydrogen generation

Hydrogen is mostly produced in conventional steam methane reforming plants. In this work, we proposed a membrane‐based reformer‐combustor reactor (MRCR) for hydrogen generation in order to improve heat recovery and overall thermal efficiency. The proposed configuration will also reduce the complexity in existing steam methane reforming (SMR) plants. The proposed MRCR comprises combustion zone, hydrogen permeate zone, and SMR zone. A computational fluid dynamics model was developed using ANSYS‐Fluent software to simulate and analyze the performance of the proposed MRCR. Results show that high hydrogen yields were observed at high reformer pressures (RPs) and low gas hourly space velocities (GHSVs). Furthermore, by increasing the steam to methane ratio and addition of excess air in the combustion side, the hydrogen yield from the MRCR decreases. This is attributed to the reduction in the effective temperature of the hydrogen membrane. High RP, low GHSV, and low steam to methane ratio that increased the hydrogen yield also decreased carbon monoxide (CO) emissions. For an increased RP from 1 to 10 bar, the CO emission decreased by about 99%. The reduction in CO emission at high RP would be attributed to the effect of water gas shift reaction in the MRCR. Results of the extensive parametric study presented in this work can be used to determine the operating conditions based on tradeoffs between hydrogen yield (mole H₂/mole CH₄), hydrogen production rate (kg of H₂/h), allowable CO emissions, and exhaust gas temperature for other applications such as gas turbine.     

Catalytic reforming of natural gas for hydrogen production in a pilot fluidized-bed membrane reactor: Mapping of operating and feed conditions

A fluidized-bed membrane reformer was operated in two independent laboratories to map various operating conditions, to investigate the effects of changing the composition of the natural gas feed stream and to verify earlier experimental trials. Two feed natural gases were tested, containing either 95.5 or 90.1 mol% of methane (3.6 or 9.9 mol% of other gaseous higher hydrocarbons). Experimental tests investigated the influence of total membrane area, reactor pressure, permeate pressure and natural gas feed rates. A permeate-H₂-to reactor natural gas feed molar ratio >2.3 was achieved with six two-sided membrane panels under steam reforming conditions and a pressure differential across the membranes of 785 kPa. The total cumulative reforming time reached 395 h, while hydrogen purity exceeded 99.99% during all tests.     

CO-free hydrogen production by steam reforming of acetic acid carried out in a Pd–Ag membrane reactor: The effect of co-current and counter-current mode

In this experimental work, a dense tubular Pd–Ag membrane reactor is used for carrying out the acetic acid steam reforming reaction for producing a CO-free hydrogen stream. The influence of the different flow configurations, as well as the sweep factor and the reaction pressure is analysed. A Ni-based commercial catalyst was packed in the lumen side of the membrane reactor and the experimental tests were performed at a reaction temperature of 400 °C and at a H₂O/acetic acid feed molar ratio of 10/1. Results in terms of CO-free hydrogen recovery, hydrogen yield and products selectivities are proposed. Moreover, a comparison between the performances of the membrane reactor and a traditional reactor working at the same operative conditions is illustrated and discussed.     

Modeling of fluidized bed membrane reactors for hydrogen production from steam methane reforming with Aspen Plus

Hydrogen production via steam methane reforming with in situ hydrogen separation in fluidized bed membrane reactors was simulated with Aspen Plus. The fluidized bed membrane reactor was divided into several successive steam methane sub-reformers and membrane sub-separators. The Gibbs minimum free energy sub-model in Aspen Plus was employed to simulate the steam methane reforming process in the sub-reformers. A FORTRAN sub-routine was integrated into Aspen Plus to simulate hydrogen permeation through membranes in the sub-separator based on Sieverts' law. Model predictions show satisfactory agreement with experimental data in the literature. The influences of reactor pressure, temperature, steam-to-carbon ratio, and permeate side hydrogen partial pressure on reactor performances were investigated with the model. Extracting hydrogen in situ is shown to shift the equilibrium of steam methane reactions forward, removing the thermodynamic bottleneck, and improving hydrogen yield while neutralizing, or even reversing, the adverse effect of pressure.