Steam reforming of n-heptane for production of hydrogen and syngas

Simultaneous production of hydrogen and syngas from the catalytic reforming of n-heptane in circulating fast fluidized bed reactors (CFFBR) and circulating fast fluidized bed membrane reactors (CFFBMR) is investigated. This paper presents modeling and simulation approach for the analysis of these reformers. Complete conversion of heptane (100%) is attained at high steam to carbon feed ratios and shorter reactor lengths by both configurations. However, the CFFBMR is very efficient in hydrogen production and can produce exit hydrogen yield up to 473.14% higher than the CFFBR. It was found that operating the CFFBMR at the optimal conditions results in a minimum value of hydrogen to carbon monoxide ratio (H₂/CO) within the recommended practical range for the syngas used as a feedstock for the gas to liquid processes (GTL). The results of the sensitivity analysis conducted for the CFFBMR has shown that the reaction side pressure and the feed temperature have significant effects on increasing the heptane conversion (up to 100%) and the temperature effect is stronger than the reaction side pressure effect. Considerable improvement in the hydrogen to carbon monoxide ratio (H₂/CO) has been achieved by increasing the reaction side pressure, while the high feed temperature has negative effect on this ratio. It seems that the practical range of H₂/CO ratio can be achieved by controlling the reformer length and the right combinations of the operating conditions.     

Discrete injection of oxygen enhances hydrogen production in circulating fast fluidized bed membrane reactors

The coupling of steam and oxidative reforming reactions of methane in a circulating fast fluidized bed membrane reactor (CFFBMR) has been studied. The study is based on rigorous modeling and simulation viewpoints. The concept of oxygen distribution has been investigated by employing the discrete injection approach. Feeding of oxygen through discrete injection points along the length of the reformer is compared with oxygen feeding through dense perovskite membranes (_{La0.4Ca0.6Fe0.8Co0.2O3-δ})$({\mathrm{La}}_{0.4}{\mathrm{Ca}}_{0.6}{\mathrm{Fe}}_{0.8}{\mathrm{Co}}_{0.2}{\mathrm{O}}_{3-\delta })$ and the conventional direct feeding of oxygen (co-feed). The results indicate that the discrete injection of oxygen enables to achieve in situ heat integration at low feed temperature. It is also shown that oxygen distribution along the length of the CFFBMR is beneficial in eliminating the hot spot temperature regions. The hydrogen yield shows an optimal value and is significantly affected by many key parameters such as feed temperature, pressure and number of hydrogen membrane tubes. The result also shows that the CFFBMR has a potential to develop complicated bifurcation behavior.     

Theoretical comparison of packed bed and fluidized bed membrane reactors for methane reforming

In this theoretical work the performance of different membrane reactor concepts, both fluidized bed and packed bed membrane reactors, has been compared for ultra-pure hydrogen production via methane reforming. Using detailed theoretical models, the required membrane area to reach a given conversion and the prevailing temperature profiles have been compared. The extent of mass and heat transfer limitations in the different reactors has been evaluated, and strategies to decrease (or avoid) these limitations have been proposed for the fluidized bed membrane reactor concept. The results show that the packed bed membrane reactor requires in some conditions double membrane area with respect to the fluidized bed membrane reactor.     

Steam reforming of propane in a fluidized bed membrane reactor for hydrogen production

Steam reforming of propane was carried out in a fluidized bed membrane reactor to investigate a feedstock other than natural gas for production of pure hydrogen. Close to equilibrium conditions were achieved inside the reactor with fluidized catalyst due to the very fast steam reforming reactions. Use of hydrogen permselective Pd₇₇Ag₂₃ membrane panels to extract pure hydrogen shifted the reaction towards complete conversion of the hydrocarbons, including methane, the key intermediate product. Irreversible propane steam reforming is limited by the reversibility of the steam reforming of this methane. To assess the performance improvement due to pure hydrogen withdrawal, experiments were conducted with one and six membrane panels installed along the height of the reactor. The results indicate that a compact reformer can be achieved for pure hydrogen production for a light hydrocarbon feedstock like propane, at moderate operating temperatures of 475–550 °C, with increased hydrogen yield.     

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.     

Steam reforming of heptane in a fluidized bed membrane reactor

n-Heptane served as a model compound to study steam reforming of naphtha as an alternative feedstock to natural gas for production of pure hydrogen in a fluidized bed membrane reactor. Selective removal of hydrogen using Pd₇₇Ag₂₃ membrane panels shifted the equilibrium-limited reactions to greater conversion of the hydrocarbons and lower yields of methane, an intermediate product. Experiments were conducted with no membranes, with one membrane panel, and with six panels along the height of the reactor to understand the performance improvement due to hydrogen removal in a reactor where catalyst particles were fluidized. Results indicate that a fluidized bed membrane reactor (FBMR) can provide a compact reformer for pure hydrogen production from a liquid hydrocarbon feedstock at moderate temperatures (475-550 °C). Under the experimental conditions investigated, the maximum achieved yield of pure hydrogen was 14.7 moles of pure hydrogen per mole of heptane fed.     

Palladium based membranes and membrane reactors for hydrogen production and purification: An overview of research activities at Tecnalia and TU/e

In this paper, the main achievements of several European research projects on Pd based membranes and Pd membrane reactors for hydrogen production are reported. Pd-based membranes have received an increasing interest for separation and purification of hydrogen. In addition, the integration of such membranes in membrane reactors has been widely studied for enhancing the efficiency of several dehydrogenation reactions. The integration of reaction and separation in one multifunctional reactor allows obtaining higher conversion degrees, smaller reactor volumes and higher efficiencies compared with conventional systems. In the last decade, much thinner dense Pd-based membranes have been produced that can be used in membrane reactors. However, the thinner the membranes the higher the flux and the higher the effect of concentration polarization in packed bed membrane reactors. A reactor concept that can circumvent (or at least strongly reduce) concentration polarization is the fluidized bed membrane reactor configuration, which improves the heat transfer as well. Tecnalia and TU/e are involved in several European projects that are related to development of fluidized bed membrane reactors for hydrogen production using thin Pd-based (<5 μm) supported membranes for different application: In DEMCAMER project a water gas shift (WGS) membrane reactor was developed for high purity hydrogen production. ReforCELL aims at developing a high efficient heat and power micro-cogeneration system (m-CHP) using a methane reforming fluidized membrane reactor. The main objective of FERRET is the development of a flexible natural gas membrane reformer directly linked to the fuel processor of the micro-CHP system. FluidCELL aims the Proof-of-Concept of a m-CHP system for decentralized off-grid using a bioethanol reforming membrane reactor. BIONICO aims at applying membrane reactors for biogas conversion to hydrogen. The fluidized bed system allows operating at a virtually uniform temperature which is beneficial in terms of both membrane stability and durability and for the reaction selectivity and yield.     

H2 production by low pressure methane steam reforming in a Pd–Ag membrane reactor over a Ni-based catalyst: Experimental and modeling

Nowadays, there is a growing interest towards pure hydrogen production for proton exchange membrane fuel cell applications. Methane steam reforming reaction is one of the most important industrial chemical processes for hydrogen production. This reaction is usually carried out in fixed bed reactors at 30–40 bar and at temperatures above 850 °C. In this work, a dense Pd–Ag membrane reactor packed with a Ni-based catalyst was used to carry out the methane steam reforming reaction between 400 and 500 °C and at relatively low pressure (1.0–3.0 bar) with the aim of obtaining higher methane conversion and hydrogen yield than a fixed bed reactor, operated at the same conditions. Furthermore, the Pd–Ag membrane reactor is able to produce a pure, or at least, a CO and CO₂ free hydrogen stream. A 50% methane conversion was experimentally achieved in the membrane reactor at 450 °C and 3.0 bar whereas, at the same conditions, the fixed bed reactor reached a 6% methane conversion. Moreover, 70% of high-purity hydrogen on total hydrogen produced was collected with the sweep-gas in the permeate stream of the membrane reactor. From a modeling point of view, the mathematical model realized for the simulation of both the membrane and fixed bed reactors was satisfactorily validated with the experimental results obtained in this work.     

Reaction/separation coupled equilibrium modeling of steam methane reforming in fluidized bed membrane reactors

An equilibrium model of steam methane reforming coupled with in-situ membrane separation for hydrogen production was developed. The model employed Sievert’s Law for membrane separation and minimum Gibbs energy model for reactions. The reforming and separation processes were coupled by the mass balance. The model assumed a continuously stirred tank reactor for the fluidized bed hydrodynamics. The model predictions for a typical case were compared with those from the model of Ye et al. [15] which assumed a plug flow for bed hydrodynamics. The model predictions show satisfactory agreement with experimental data in the literatures. The influences of reactor pressure, temperature, steam to carbon ratio, and permeate side hydrogen partial pressure on solid carbon, NH_x and NO_x formation were studied using the model.     

Experiments on hydrogen production from methanol steam reforming in fluidized bed reactor

A novel approach for the hydrogen production which integrated methanol steam reforming and fluidized bed reactor (FBR) was proposed. The reaction was carried out over Cu/ZnO/Al₂O₃ catalysts. The critical fluidized velocities under different catalyst particle sizes and masses were obtained. The influences of the operating parameters, including that of H₂O-to-CH₃OH molar ratio, feed flow rate, reaction temperature, and catalyst mass on the performance of methanol steam reforming were investigated in FBR to obtain the optimum experimental conditions. More uniform temperature distribution, larger surface volume ratio and longer contacting time can be achieved in FBR than that in fixed bed reactor. The results indicate that the methanol conversion rate in FBR can be as high as 91.95% while the reaction temperatures is 330 °C, steam-to-carbon molar ratio is 1.3, and feed flow rate is 540 ml/h under the present experiments, which is much higher than that in the fixed bed.     

Numerical studies of sorption-enhanced glycerol steam reforming in a fluidized bed membrane reactor at low temperature

In order to improve the hydrogen production efficiency by glycerol steam reforming, a membrane-assisted fluidized bed reactor with carbon dioxide sorption is developed to enhance the reforming process. Low-temperature operation in a membrane reactor is necessary considering the thermal stability of membrane. In this work, the sorption-enhanced glycerol steam reforming process in a fluidized bed membrane reactor under the condition of low temperature is numerically investigated, where the hydrotalcite is employed as CO₂ sorbents. The impact of operating pressure on the reforming performance is further evaluated. The results demonstrate that the integration of membrane hydrogen separation and CO₂ sorption can effectively enhance the low-temperature glycerol reforming performance. The fuel conversion above 95% can be achieved under an elevated pressure.     

Pure hydrogen production via autothermal reforming of ethanol in a fluidized bed membrane reactor: A simulation study

In this paper the production of ultra-pure hydrogen via autothermal reforming of ethanol in a fluidized bed membrane reactor has been studied. The heat needed for the steam reforming of ethanol is obtained by burning part of the hydrogen recovered via the hydrogen perm-selective membrane thereby integrating CO₂ capture. Simulation results based on a phenomenological model show that it is possible to obtain overall autothermal reforming of ethanol while 100% of hydrogen can in principle be recovered at relatively high temperatures and at high reaction pressures. At the same operating conditions, ethanol is completely converted, while the methane produced by the reaction is completely reformed to CO, CO₂ and H₂.     

Production of a hydrogen-rich gas from fast pyrolysis bio-oils: Comparison between homogeneous and catalytic steam reforming routes

The aim of the present work is to produce hydrogen from biomass through bio-oil. Two possible upgrading routes are compared: catalytic and non-catalytic steam reforming of bio-oils. The main originality of the paper is to cover all the steps involved in both routes: the fast pyrolysis step to produce the bio-oils, the water extraction for obtaining the bio-oil aqueous fractions and the final steam reforming of the liquids. Two reactors were used in the first pyrolysis step to produce bio-oils from the same wood feedstock: a fluidized bed and a spouted bed. The mass balances and the compositions of both batches of bio-oils and aqueous fractions were in good agreement between both processes. Carboxylic acids, alcohols, aldehydes, ketones, furans, sugars and aromatics were the main compounds detected and quantified. In the steam reforming experiments, catalytic and non-catalytic processes were tested and compared to produce a hydrogen-rich gas from the bio-oils and the aqueous fractions. Moreover, two different catalytic reactors were tested in the catalytic process (a fixed and a fluidized bed). Under the experimental conditions tested, the H₂ yields were as follows: catalytic steam reforming of the aqueous fractions in fixed bed (0.17 g H₂/g organics) > non-catalytic steam reforming of the bio-oils (0.14 g H₂/g organics) > non-catalytic steam reforming of the aqueous fractions (0.13 g H₂/g organics) > catalytic steam reforming of the aqueous fractions in fluidized bed (0.07 g H₂/g organics). These different H₂ yields are a consequence of the different temperatures used in the reforming processes (650 °C and 1400 °C for the catalytic and the non-catalytic, respectively) as well as the high spatial velocity employed in the catalytic tests, which was not sufficiently low to reach equilibrium in the fluidized bed reactor.     

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.     

Hydrogen production by chemical-looping reforming in a circulating fluidized bed reactor using Ni-based oxygen carriers

This work presents the experimental results obtained during auto-thermal chemical-looping reforming (CLR) in a 900 W_th circulating fluidized bed reactor under continuous operation using methane as fuel. Two oxygen carriers based on NiO and supported on γ-Al₂O₃ and α-Al₂O₃ were used during more than 50 h of operation with each oxygen carrier. During operation the effect of different operating variables, like fuel reactor temperature, H₂O/CH₄ molar ratio and solid circulation rate, on CH₄ conversion and gas product distribution was analyzed. It was found that in all operating conditions CH₄ conversion was very high (>98%) and the most important variable affecting to the gas product distribution was the solid circulation rate, that is, NiO/CH₄ molar ratio. Similar gas product distribution was obtained working with both oxygen carriers although at different NiO/CH₄ molar ratios. The oxygen carrier of NiO on α-Al₂O₃ needed lower NiO/CH₄ molar ratio to reach the same gas product composition than the oxygen carrier of NiO on γ-Al₂O₃. Working at optimal operating conditions, 2.5 moles of H₂ per mol of CH₄ could be obtained in this process.During operation the oxygen carrier particles maintained their physical and chemical properties. These results suggest that these oxygen carriers could have a high durability, being suitable oxygen carriers for a CLR system.     

Glycerol steam reforming in a bench scale continuous flow heat recovery reactor

In the present study glycerol was successfully gasified using a diesel engine waste heat recovery system obtaining hydrogen and methane rich gaseous products. The reforming reactor was equipped with a vaporization pre-chamber to ensure uniform reactants distribution and a fixed reaction bed, being mounted in countercurrent flow configuration with the engine combustion gases stream. Accordingly, the reactions were conducted at gradually increased temperature conditions; starting at around 300 °C in the top section of the reaction bed and finishing in a controlled outlet bed temperature of 600–800 °C. When compared to homogeneous temperature reactors, the configuration used here produced a syngas of higher methane and ethylene contents. With regards to the reactor performance, syngas lower heat values of more than 22 MJ/kg were achieved with glycerol feed concentrations within 50–70% and outlet bed temperatures above 700 °C, corresponding to cold gas efficiencies of around 85%. The present results indicate that glycerin can be utilized as a syngas feedstock for steam reforming processes based on waste heat recovery.     

Thermo-catalytic decomposition of propane over carbon black in a fluidized bed for hydrogen production

Thermo-catalytic decomposition of propane to solid carbon and hydrogen was examined for hydrogen production without CO₂ emission. The reaction was carried out over a carbon black catalyst in a bench-scale fluidized bed reactor. Effects of reaction temperature on the propane conversion and product distribution were examined. Catalytic activity of the carbon black was maintained stable for longer than 8 h in spite of carbon deposition. From 600 to 650 °C, the propane conversion increased sharply with propylene produced in a considerably larger amount than methane. As the reaction temperature further increased up to 800 °C, the major hydrocarbon product was methane; the production of propylene decreased rapidly and ethylene was the next most abundant product. The surface area of the carbon black was decreased as the reaction proceeded due to carbon deposition. Surface morphology of the used carbon black was observed by TEM and the change of the aggregates size was measured.     

循环流化床锅炉优点分析

循环流化床锅炉因具有燃料适应性广、负荷调节性强以及环保性能优良而日益得到人们的重视,并且是传统技术所无法实现的,正是由于这些技术优点,使循环流化床锅炉得以快速发展和广泛应用.     

Dry reforming of methane has no future for hydrogen production: Comparison with steam reforming at high pressure in standard and membrane reactors

The methane dry-reforming and steam reforming reactions were studied as a function of pressure (1–20 atm) at 973 K in conventional packed-bed reactors and a membrane reactors. For the dry-reforming reaction in a conventional reactor the production yield of hydrogen rose and then decreased with increasing pressure as a result of the reverse water-gas shift reaction in which the hydrogen reacted with the reactant CO₂ to produce water. For the steam reforming reaction the production yield of hydrogen kept increasing with pressure because the forward water-gas shift reaction produced additional hydrogen by the reaction of CO with water. In the membrane reactors the methane conversion and the hydrogen production yields were higher for both the dry-reforming and steam reforming reactions, but for the dry reforming at high pressure half of the hydrogen was transformed into water. Thus, the dry-reforming reaction is not practical for producing hydrogen.     

Mini CHP based on the electrochemical generator and impeded fluidized bed reactor for methane steam reforming

The paper presents a configuration of mini CHP with the methane reformer and planar solid oxide fuel cell (SOFC) stacks. This mini CHP may produce electricity and superheated steam as well as preheat air and methane for the reformer along with cathode air used in the SOFC stack as an oxidant. Moreover, the mathematical model for this power plant has been created. The thermochemical reactor with impeded fluidized bed for autothermal steam reforming of methane (reformer) considered as the basis for the synthesis gas (syngas) production to fuel SOFC stacks has been studied experimentally as well. A fraction of conversion products has been oxidized by the air fed to the upper region of the impeded fluidized bed in order to carry out the endothermic methane steam reforming in a 1:3 ratio as well as to preheat products of these reactions. Studies have shown that syngas containing 55% of hydrogen could be produced by this reactor. Basic dimensions of the reactor as well as flow rates of air, water and methane for the conversion of methane have been adjusted through mathematical modelling.The paper provides heat balances for the reformer, SOFC stack and waste heat boiler (WHB) intended for generating superheated water steam along with preheating air and methane for the reformer as well as the preheated cathode air. The balances have formed the basis for calculating the following values: the useful product fraction in the reformer; fraction of hydrogen oxidized at SOFC anode; gross electric efficiency; anode temperature; exothermic effect of syngas hydrogen oxidation by air oxygen; excess entropy along with the Gibbs free energy change at standard conditions; electromotive force (EMF) of the fuel cell; specific flow rate of the equivalent fuel for producing electric and heat energy. Calculations have shown that the temperature of hydrogen oxidation products at SOFC anode is 850 °C; gross electric efficiency is 61.0%; EMF of one fuel cell is 0.985 V; fraction of hydrogen oxidized at SOFC anode is 64.6%; specific flow rate of the equivalent fuel for producing electric energy is 0.16 kg of eq.f./(kW·h) while that for heat generation amounts to 44.7 kg of eq.f./(GJ). All specific parameters are in agreement with the results of other studies.