CFD analysis on sorption-enhanced glycerol reforming in a membrane-assisted fluidized bed reactor

In this work, a three-dimensional simulation of the sorption-enhanced glycerol reforming (SEGR) process for hydrogen production in a membrane-assisted fluidized bed reactor is carried out by means of the multi-fluid model coupling with chemical kinetics model and membrane separation model. The mutual interaction mechanism of the two enhancing methods including membrane hydrogen separation and carbon dioxide sorption is revealed. The results indicate that the carbon dioxide sorption can hinder the concentration polarization resistance and improve the hydrogen permeation rate while the scope of densified zones is enlarged. Meanwhile, the increase of hydrogen separation degree is also beneficial to the carbon dioxide sorption performance. In addition, the utilization of bi-functional sorbent-catalyst particles can further promote the sorption-enhanced reforming process compared to the conventional two-pellet design.     

Enhancement of membrane hydrogen separation on glycerol steam reforming in a fluidized bed reactor

Membrane hydrogen separation can effectively promote fuel conversion and hydrogen yield by means of altering chemical equilibrium of reforming reactions. In this work, the enhancing process of glycerol steam reforming via a fluidized bed membrane reactor is numerically investigated. Under the framework of the Euler-Euler method, chemical kinetic model is implemented and the reforming performance with and without membrane separation is compared. The effect of densified zones caused by membrane separation is examined. Meanwhile, the impacts of operating parameters including hydrogen partial pressure on the permeate side and fuel gas velocity on densified zones and hydrogen yield are evaluated. The results demonstrate that the excessive reduction of hydrogen partial pressure on the permeate side and the increase of feed gas velocity are detrimental to fuel conversion and hydrogen yield.     

Performance evaluation of PdAg membrane reactor in glycerol steam reforming process: Development of the CFD model

In the present paper, a CFD modeling of palladium membrane reactor, in which hydrogen produced through glycerol steam reforming, is presented. A comprehensive and precise kinetic and permeation model was used. On the basis of the equations and assumptions, an excellent agreement between model prediction and experimental data was achieved. Pressure, velocity and concentration distribution of various component within the Membrane Reactor (MR) were predicted. Moreover, the performance of both a Traditional Reactor (TR) and a MR was compared in various condition. The effects of some operating conditions such as temperature, pressure, feed flow rate and flow pattern on the glycerol conversion, hydrogen recovery and CO selectivity were evaluated. The most effective parameter was pressure: increasing it from 1 to 10 bar in co-current MR, the glycerol conversion, H2 recovery and CO selectivity were shifted from 46%, 17% and 6.6%–81%, 56% and 0.8%, respectively. The CFD model indicates that the performance of glycerol steam reforming improves when MR is used instead of TR. At various operating conditions the glycerol convertion enhanced 10–64% and CO selectivity reduced 7.5–99.0% in the MR when compared with the TR.     

Exergy analysis of glycerol steam reforming in a heat recovery reactor

A detailed exergy analysis was performed for the steam reforming process of glycerol by means of a series of experiments in a bench scale apparatus. The reforming was conducted in a fixed bed reactor, which operated in heat recovery mode by extracting the demanded energy from hot exhaust gases provided by a diesel engine. In order to determine the role of the main operational parameters into the exergy efficiency of the studied process, the experiments were carried out with glycerol feed concentrations in water ranging from 10% up to 90% weight, whereas the outlet reactor temperature was varied from 600 °C up to 800 °C. Detailed exergy balances revealed a compromise between the exergy destruction within the reforming reactor and liquid separator versus the exergy losses associated to the tar and char outputs. This trade-off was favourable to the 50% and 70% glycerol feed concentration regimes and plateaus of about 74% exergy efficiency and 24 MJ/kg dry syngas exergy content were verified from 650 to 800 °C reactor temperatures.     

A CFD approach on simulation of hydrogen production from steam reforming of glycerol in a fluidized bed reactor

Hydrogen production from steam reforming of glycerol in a fluidized bed reactor has been simulated using a CFD method by an additional transport equation with a kinetic term. The Eulerian–Eulerian two-fluid approach was adopted to simulate hydrodynamics of fluidization, and chemical reactions were modelled by laminar finite-rate model. The bed expansion and pressure drop were predicted for different inlet gas velocities. The results showed that the flow system exhibited a more heterogeneous structure, and the core-annulus structure of gas–solid flow led to back-mixing and internal circulation behaviour, and thus gave a poor velocity distribution. This suggests the bed should be agitated to maintain satisfactory fluidizing conditions. Glycerol conversion and H₂ production were decreased with increasing inlet gas velocity. The increase in the value of steam to carbon molar ratio increases the conversion of glycerol and H₂ selectivity. H₂ concentrations in the bed were uneven and increased downstream and high concentrations of H₂ production were also found on walls. The model demonstrated a relationship between hydrodynamics and hydrogen production, implying that the residence time and steam to carbon molar ratio are important parameters. The CFD simulation will provide helpful data to design and operate a bench scale catalytic fluidized bed reactor.     

Conversion of biodiesel synthesis waste to hydrogen in membrane reactor: Theoretical study of glycerol steam reforming

Hydrogen production from waste glycerol, mainly producible as a by-product of biodiesel synthesis, is investigated as an attractive opportunity for exploiting renewable energy sources for further applications. Glycerol steam reforming using membrane technology was modeled by taking into accounts the maim transport phenomena, thermodynamic criteria and chemical process kinetics. A sensitivity analysis of operating conditions was made for key performance metrics such as glycerol conversion, hydrogen yield and hydrogen recovery. Glycerol conversion intensifies with enhancement of operating pressure and temperature, whereas high feed molar ratio and sweep ratio have limiting effect. Hydrogen permeation and subsequently, hydrogen recovery facilitates with increasing sweep gas ratio and sweep gas temperature. Hydrogen recovery enhances from 70% to 99% with increasing temperature from 350 to 500 °C at feed molar ratio of 3. Also, hydrogen recovery improves from 50% to 71% with increasing sweep ratio from 0 to 20 at 350 °C and 1 bar.     

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming in a tubular fixed-bed reactor

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming (SE-SMR) in a tubular fixed-bed reactor with a constant wall temperature of 600 °C is investigated numerically by an experimentally verified unsteady two-dimensional model. The reactor uses Ni/Al₂O₃ as the reforming catalyst and CaO as the sorbent. The reaction of SMR is enhanced by removing the CO₂ through the reaction of CaO + CO₂ → CaCO₃ based on the Le Chatelier's principle. A non-uniform temperature distribution instead of a uniform temperature in the reactor appears due to the rapid endothermic reaction of SMR followed by an exothermic reaction of CO₂ sorption. For a small weight hourly space velocity (WHSV) of 0.67 h^?1 before the CO₂ breakthrough, both a low and a high temperature regions exist simultaneously in the catalyst/sorbent bed, and their sizes are enlarged and the temperature distribution is more non-uniform for a larger tube diameter (D). Both the CH₄ conversion and the H₂ molar fraction are slightly increased with the increase of D. Based on the parameters adopted in this work, the CH₄ conversion, the H₂ and CO molar fractions at D = 60 mm are 84.6%, 94.4%, and 0.63%, respectively. After CO₂ breakthrough, the reaction of SMR dominates, and the reactor performance is remarkably reduced due to low reactor temperature.For a higher value of WHSV (4.03 h^?1) before CO₂ breakthrough, both the reaction times for SMR and CO₂ sorption become much shorter. The size of low temperature region becomes larger, and the high temperature region inside the catalyst/sorbent bed doesn't exist for D ≥ 30 mm. The maximum temperature difference inside the catalyst/sorbent bed is greater than 67 °C. Both the CH₄ conversion and H₂ molar fraction are slightly decreased with the increase of D. However, this phenomenon is qualitatively opposite to that for small WHSV of 0.67 h^?1. The CH₄ conversion and H₂ molar fraction at D = 60 mm are 52.6% and 78.7%, respectively, which are much lower than those for WHSV = 0.67 h^?1.     

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.     

Continuous sorption-enhanced steam reforming of glycerol to high-purity hydrogen production

In this study, the continuous sorption-enhanced steam reforming of glycerol to high-purity hydrogen production by a simultaneous flow concept of catalyst and sorbent for reaction and regeneration using two moving-bed reactors has been evaluated experimentally. A Ni-based catalyst (NiO/NiAl₂O₄) and a lime sorbent (CaO) were used for glycerol steam reforming with and without in-situ CO₂ removal at 500 °C and 600 °C. The simultaneous regeneration of catalyst and sorbent was carried out with the mixture gas of N₂ and steam at 900 °C. The product gases were measured by a GC gas analyzer. It is obvious that the amounts of CO₂, CO and CH₄ were reduced in the sorption-enhanced steam reforming of glycerol, and the H₂ concentration is greatly increased in the pre-CO₂ breakthrough periods within 10 min both 500 °C and 600 °C. The extended time of operation for high-purity hydrogen production and CO₂ capture was obtained by the continuous sorption-enhanced steam reforming of glycerol. High-purity H₂ products of 93.9% and 96.1% were produced at 500 °C and 600 °C and very small amounts of CO₂, CH₄ and CO were formed. The decay in activity during the continuous reaction-regeneration of catalyst and sorbent was not observed.     

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.     

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.     

Integration of sorption-enhanced steam glycerol reforming with methanation of in-situ removed carbon dioxide - An alternative for glycerol valorization

Coupling CO₂ desorption and methanation in the presence of hybrid materials offers a promising alternative to convert the CO₂ in-situ removed during sorption-enhanced steam glycerol reforming (SESGR) avoiding the high energy-intensive CO₂ sorbent regeneration. The all-inclusive integrated process exemplifies an option for glycerol valorization via consecutive SESGR and CO₂ conversion by catalytic hydrogenation. The dual-function catalyst performing successively, in the same reactor, SESGR and CO₂ desorption/conversion encompasses reforming/methanation catalyst (10%Ni5%Co) and dispersed nano-sized CaO on γ-Al₂O₃. Simultaneous CO₂ desorption/conversion integrated process is explored in a fixed-bed reactor via an unsteady-state, two-scale, non-isothermal model, highlighting the impact of key parameters on the process performance. At large adsorbent/catalyst mass ratio (2.0) and high CaO conversion (0.5) in preceding SESGR, CO₂ is released and hydrogenated for an extended period with extra hydrogen consumption, without a balance between CO₂ desorption and CO₂ hydrogenation rates. Increasing pressure (3.0 MPa) and gas velocity offers a match between these competitive reaction rates, resulting low CO₂ concentration in the exit stream. Desorption/methanation thermal behavior controls the magnitude of CO₂ low concentration period and the methanation efficiency.     

Coke deactivation of Ni and Co catalysts in ethanol steam reforming at mild temperatures in a fluidized bed reactor

The deactivation by coke deposition of Ni and Co catalysts in the steam reforming of ethanol has been studied in a fluidized bed reactor under the following conditions: 500 and 700 °C; steam/ethanol molar ratio, 6; space time, 0.14 g_catalyst h/g_ethanol, partial pressure of ethanol in the feed, 0.11 bar, and time on stream up to 20 h. The decrease in activity depends mainly on the nature of the coke deposited on the catalysts, as well as on the physical–chemical properties (BET surface area, pore volume, metal surface area) of the catalysts. At 500 °C (suitable temperature for enhancing the WGS reaction, decreasing energy requirements and avoiding Ni sintering), the main cause of deactivation is the encapsulating coke fraction (monoatomic and polymeric carbon) that blocks metallic sites, whereas the fibrous coke fraction (filamentous carbon) coats catalyst particles and increases their size with time on stream with a low effect on deactivation, especially for catalysts with high surface area. The catalyst with 10 wt% Ni supported on SiO₂ strikes a suitable balance between reforming activity and stability, given that both the capability of Ni for dehydrogenation and C–C breakage and the porous structure of SiO₂ support enhance the formation of filamentous coke with low deactivation. This catalyst is suitable for use at 500 °C in a fluidized bed, in which the collision among particles causes the removal of the external filamentous coke, thus minimizing the pore blockage of the SiO₂. At 700 °C, the coke content in the catalyst is low, with the coke being of filamentous nature and with a highly graphitic structure.     

Transient reaction phenomena of sorption-enhanced steam methane reforming in a fixed-bed reactor

The transient chemical reaction phenomena of the sorption-enhanced steam methane reforming (SE-SMR) by using Ni/Al₂O₃ catalyst and CaO sorbent in a tubular fixed-bed reactor were numerically investigated by an experimentally verified unsteady 2D model. Four chemical reactions are involved in SE-SMR including steam reforming (SR), water gas shift (WGS), global steam reforming (GSR), and CO₂ sorption. The reaction process in time is divided into period 1, transient period, and period 2. The high-purity H₂ is produced in period 1 which is defined as the outlet molar fractions of H₂ ≥ 90% and CO ≤ 1% (dry basis) in this work. In the first half of period 1, the endothermic reaction rates of SR and GSR are dominant in the entrance region of catalyst/sorbent bed. The WGS and CO₂ sorption reactions are triggered by SR and GSR reactions. The heat transfer from the wall plays an important role. Higher CaO conversion, temperature, and reaction rates appear first near the wall region, then they gradually expand to the central region.In the second half of period 1, a sharp wave-shaped curve of strong CO₂ sorption reaction occurred in downstream becomes dominant and it moves to downstream almost at a constant speed, as time progresses. The peak value of the CO₂ sorption reaction is more than twice larger than that of SR or WGS. The SR and WGS reaction rates are significantly enhanced by CO₂ sorption reaction. The great sorption, WGS, and SR reactions result in a high-purity H₂ production with the outlet molar fractions of 95.8% H₂, 0.998% CO, and 0.73% CO₂ at the end of period 1, based on the parameters used in this work such as reactor temperature of 600 °C. The maximum CaO conversion is about 76% in end of period 1 and the average CaO conversion in the reactor is 51%. The 2D distributions of CaO conversion, temperature, and reaction rates are also presented and discussed.     

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.     

Effects of attapulgite-supported transition metals catalysts on glycerol steam reforming for hydrogen production

The attapulgite supported transition metals (Ni, Cu, Co or Fe) catalysts were prepared by precipitation method at constant loading (10 wt%) and investigated in the glycerol steam reforming reaction for H₂ production under 400–750 °C, water/glycerol (W/G) = 3, N₂ flow ratio = 0.16 L/min and WHSV = 6.46 h^?1. The as-prepared catalysts were characterized by N₂ adsorption-desorption, XRD, H₂-TPR and TEM-EDS. The results shown different active metals presented various crystalline sizes and reduction properties. The experimental results revealed Ni/ATP and Co/ATP catalysts had more active for glycerol steam reforming than Cu/ATP and Fe/ATP catalysts, due to the fact that active metal Ni and Co have superior capacity to promote the necessary CC rupture and facilitate the water gas shift reaction. In addition, the results revealed that CH₄ production was favored at low temperatures while CO production was presented at high temperatures, which were induced by the different reaction networks over catalysts. In addition, the stability test shown all catalysts had different various degrees of inactivation, resulting from the sintering of active metals and carbon deposition. The characterizations of XRD, TEM and TG-DTG for spent catalysts revealed the smallest amount of carbon deposited for Cu/ATP, which was attributed to the lowest Cu particle size. Additionally, two different types of carbon was found, namely filamentous carbon for Ni and Co/ATP and encapsulating carbon for Cu and Fe/ATP.     

Hydrogen production for PEM fuel cell by gas phase reforming of glycerol as byproduct of bio-diesel. The use of a Pd-Ag membrane reactor at middle reaction temperature

Glycerol as a byproduct of biodiesel production represents a renewable energy source. In particular, glycerol can be used in the field of hydrogen production via gas phase reforming for proton exchange membrane fuel cell (PEMFC) applications. In this work, glycerol steam reforming (GSR) reaction was investigated using a dense palladium-silver membrane reactor (MR) in order to produce pure (or at least CO-free) hydrogen, using 0.5 wt% Ru/Al₂O₃ as reforming catalyst. The experiments are performed at 400 °C, water to glycerol molar feed ratio 6:1, reaction pressure ranging from 1 to 5 bar and weight hourly space velocity (WHSV) from 0.1 to 1.0 h⁻¹. Moreover, a comparative study is given between the Pd-Ag MR and a traditional reactor (TR) working at the same MR operating conditions. The effect of the WHSV and reaction pressure on the performances of both the reactors in terms of glycerol conversion and hydrogen yield is also analyzed. The MR exhibits higher conversion than the TR (∼60% as best value for the MR against ∼40% for the TR, at WHSV = 0.1 h⁻¹ and 5 bar), and high CO-free hydrogen recovery (around 60% at WHSV = 0.1 h⁻¹ and 5 bar). During reaction, carbon coke is formed limiting the performances of the reactors and inhibiting, in particular, the hydrogen permeation through the membrane with a consequent reduction of hydrogen recovery in the permeate side.     

Steam reforming of methane in a tapered membrane - Assisted fluidized - Bed reactor: Modeling and simulation

A compartment model was developed to describe the flow pattern of gas within the dense zone of a tapered membrane-assisted fluidized-bed reactor (TMAFBR), in the bubbling mode of operation for steam reforming of methane under wall heat flux. The parameters of the developed model (i.e., number of compartments for the bubble and emulsion phases) were determined using the experimental data reported elsewhere [Adris AM, Lim CJ, Grace JR. The fluidized bed membrane reactor system: a pilot scale experimental study. Chem Eng Sci 1994; 49:5833-43.] and good agreements were obtained between model predictions and corresponding experimental data. The developed model was then utilized to predict the behavior of TMAFBR under various operating and design conditions. Moreover, the influences of tapered angle, bed operating temperature and pressure, and feed temperature on the methane conversion and the total yield of hydrogen were carefully investigated. Furthermore, the performance capability of the TMAFBR was compared with that of a columnar one under identical operating conditions.