Application of aspen plus to renewable hydrogen production from glycerol by steam reforming

Steam reforming is the most favored method for the production of hydrogen. Hydrogen is mostly manufactured by using steam reforming of natural gas. Due to the negative environmental impact and energy politics, alternative hydrogen production methods are being explored. Glycerol is one of the bio-based alternative feedstock for hydrogen production. This study is aimed to simulate hydrogen production from glycerol by using Aspen Plus. First of all, the convenient reactor type was determined. RPlug reactor exhibited the highest performance for the hydrogen production. A thermodynamic model was determined according to the formation of byproduct. The reaction temperature, water/glycerol molar feed ratio as reaction parameters and reactor pressure were investigated on the conversion of glycerol and yield of hydrogen. Optimum reaction parameters are determined as 500 °C of reaction temperature, 9:1 of water to glycerol ratio and 1 atm of pressure. Reactor design was also examined. Optimum reactor diameter and reactor length values were determined as 5 m and 50 m, respectively. Hydrogen purification was studied and 99.9% purity of H₂was obtained at 25 bar and 40 °C. The obtained results were shown that Aspen Plus has been successfully applied to investigate the effects of reaction parameters and reactor sizing for hydrogen production from glycerol steam reforming.     

Application of catalytic membrane reactor for pure hydrogen production by flare gas recovery as a novel approach

In the present study, application of catalytic membrane reactor as a novel approach for the flare gas recovery is proposed. A comprehensive two-dimensional non-isothermal model has been constructed to evaluate the performance of flare gas recovery process in the membrane reactor. The model is developed by taking into accounts the main chemical kinetics, heat and mass transfer phenomena and hydrogen permeation in the radial direction across a Pd–Ag membrane. The model predictions are validated based on different experimental results reported in literature. The impact of reactor operating conditions on the recovery process such as temperature and pressure, feed molar ratio and sweep gas ratio are investigated and discussed. The modeling results confirm that the flare gas conversion and hydrogen recovery improves with increasing the operating temperature, pressure and sweep ratio as a consequence of increasing the driving force for H₂ permeation through membrane. The environmental consideration revealed that by application of catalytic membrane reactor for the flare gas recovery of Asalouyeh gas processing plant (Iran), not only the equivalent mass of greenhouse gases emission reduces from 2179 kg/s to 36 kg/s, but also, 12.7 kg/s pure hydrogen will be produced by flare gas recovery at 750 K, 5 bar, sweep ratio of 5 and feed molar ratio of 4.     

Parametric study of membrane reactors for hydrogen production via high-temperature water gas shift reaction

This study presents numerical studies of hydrogen production performance via water gas shift reaction in membrane reactor. The pre-exponential factor in describing the hydrogen permeation flux is used as the main parameter to account for the membrane permeance variation. The operating pressure, temperature and H₂O/CO molar ratio are chosen in the 1–20 atm, 400–600 °C and 1–3 ranges, respectively. Based on the numerical simulation results three distinct CO conversion regimes exist based on the pre-exponential factor value. For low pre-exponential factors corresponding to low membrane permeance, the CO conversion approaches to that obtained from a conventional reactor without hydrogen removal. For high pre-exponential factor, high CO conversion and H₂ recovery with constant values can be obtained. For intermediate pre-exponential factor range both CO conversion and H₂ recovery vary linearly with the pre-exponential factor. In the high membrane permeation case CO conversion and H₂ recovery approach limiting values as the operating pressure increases. Increasing the H₂O/CO molar ratio results in an increase in CO conversion but decrease in H₂ recovery due to hydrogen permeation driving force reduction. As the feed rate increases in the reaction side both the CO conversion and hydrogen recovery decrease because of decreased reactant residence time. The sweep gas flow rate has a significant effect on hydrogen recovery. Low sweep gas flow rate results in low CO conversion H₂ recovery while limiting CO conversion and hydrogen recovery can be reached for the high membrane permeance and high sweep gas flow rate cases.     

Hydrogen production from supercritical water reforming of glycerol in an empty Inconel 625 reactor

Glycerol reforming was investigated under supercritical water conditions (450–575 °C, 250 bar). A feed containing 5 wt.% of glycerol was continuously fed to an empty Inconel 625 reactor. The products of the reaction were separated into gas and liquid phases in a condenser. At a feed rate of 2.15 g/min, the glycerol conversion significantly increased from 0.05 to 0.97 when increasing operating temperature from 450 to 575 °C. Although lowering the feed rate (i.e. increasing the residence time) could considerably improve the conversion, carbon formation became a problem especially at high operating temperatures (550–575 °C). The major gaseous products were hydrogen (approximately 60 mol%), carbon monoxide, carbon dioxide and methane with some traces of ethane, ethylene, propane, and propylene. Various liquid products were detected including acetaldehyde, acetol, methanol, acetic acid, propionaldehyde, allyl alcohol, acetone, acrolein, ethanol, ethylene glycol, and acrylic acid but the major liquid components were acetaldehyde and acetol. With a feed glycerol concentration of 2.5 wt.% and operating temperature of 525 °C, glycerol conversion of 0.91 and H₂ yield of 2.86 can be obtained without carbon formation. Finally, it was demonstrated that higher H₂ yield with much lower carbon formation was observed in supercritical water reforming (250 bar) compared to conventional steam reforming at 1 bar under similar temperatures.     

Thermodynamic analyses of adsorption-enhanced steam reforming of glycerol for hydrogen production

A non-stoichiometric thermodynamic analysis is performed on the adsorption-enhanced steam reforming of glycerol for hydrogen production based on the principle of minimising the Gibbs free energy. The effects of temperature (600–1000 K), pressure (1–4 bar), water to glycerol feed ratio (3:1–12:1), percentage of CO₂ adsorption (0–99%) and molar ratio of carrier gas to feed reactants (1:1–5:1) on the reforming reactions and carbon formation are examined. The results show that the use of a CO₂ adsorbent enhances glycerol conversion to hydrogen and the maximum number of moles of hydrogen produced per mole of glycerol can be increased from 6 to 7 due to the CO₂ adsorption. The analyses suggest that the most favourable temperature for steam–glycerol reforming is between 800 and 850 K in the presence of a CO₂ adsorbent, which is about 100 K lower than that for reforming without CO₂ adsorption. Although high pressures are favourable for CO₂ adsorption, a lower operating pressure gives a higher overall hydrogen conversion. The most favourable water to glycerol feed ratio is found to be 9.0 above which the benefit becomes marginal. Carbon formation could occur at low water to glycerol feed ratios, and the use of a CO₂ adsorbent can suppress the formation reaction and substantially reduce the lower limit of the water to glycerol feed ratio for carbon formation.     

CFD modelling of supercritical water reforming of glycerol for hydrogen production

Glycerol, as a main by-product of biodiesel synthesis, can be used in a large variety of applications including food, personal care, pharmaceutical and chemical industries However, due to the large production of biodiesel, the glycerol market was depressed. The conversion of glycerol into an energy carrier (syngas or hydrogen) could be a very interesting route to providing value as a renewable energy source. The reforming of glycerol leads to an almost complete conversion and very high carbon-to-gas efficiency with short residence time.In this work, the performances of packed bed reactor for hydrogen production from glycerol in supercritical conditions, by using a Ni-based catalyst supported on Al₂O₃ and SiO₂, through CFD modelling in three-dimensions were studied. The parameters of kinetic model were determined by using an optimization method to fit the experimental data. The developed model was been validated based on experimental results published in literature for three different feed concentration of glycerol of 5, 10 and 20 wt% (R² = 0.969).Varying the reaction temperature, between 500 and 800 °C, and residence time, between 1.5 and 10 s, the concentration of hydrogen increased with increasing the temperature and decreasing the residence time. At high temperature, the hydrogen can achieve a concentration of 65% and the present of methane is less than 5% and carbon monoxide maintain lower concentration. The simulation results show that high hydrogen yield can be obtained in short residence time with conversion of glycerol almost completed.     

A mixed electronic and protonic conducting hydrogen separation membrane with asymmetric structure

In this work, highly doped ceria with lanthanum, La_0.5Ce_0.5O_2−δ (LDC), are developed as hydrogen separation membrane material. LDC presents a mixed electronic and protonic conductivity in reducing atmosphere and good stability in moist CO₂ environment. LDC separation membranes with asymmetrical structure are fabricated by a cost-saving co-pressing method, using NiO + LDC + corn starch mixture as substrate and LDC as top membrane layer. Hydrogen permeation properties are systemically studied, including the influence of operating temperature, hydrogen partial pressure in feed stream and water vapor in both sides of the membrane on hydrogen permeating fluxes. Hydrogen permeability increases as the increasing of temperature and hydrogen partial pressure in feed gas. Using 20% H₂/N₂ (with 3% of H₂O) as feed gas and dry high purity argon as sweep gas, an acceptable flux of 2.6 × 10⁻⁸ mol cm⁻² s⁻¹ is achieved at 900 °C. The existing of water in both sides of membrane has significant effect on hydrogen permeation and the corresponding reasons are analyzed and discussed.     

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.     

A comparative study on hydrogen production from steam-glycerol reforming: thermodynamics and experimental

A detailed comparative study on thermodynamic and experimental analyses of glycerol reforming for hydrogen production has been conducted in terms of the effects of temperature, pressure, water to glycerol feed ratio, feeding reactants to inert gas ratio and feeding gas flow rate (residence time). The thermodynamic analysis was conducted by using a non-stoichiometric methodology based on the minimisation of Gibbs free energy. And the experiments were carried out with a pilot scale set-up. The results show that the thermodynamic and experimental data agree fairly well with each other. The measured hydrogen production is slightly lower than that predicted by the thermodynamic analysis, which is mainly because the conversion of steam is incomplete. High temperature, low pressure, low feeding reactants to inert gas ratio and low gas flow rate are favourable for steam reforming of glycerol for hydrogen production. There is an optimal water to glycerol feed ratio for steam reforming of glycerol for hydrogen production which is about 9.0. The glycerol conversion is a strong function of water to glycerol ratio, whereas a weak function of other parameters over the conditions of this work. A novel adsorption enhanced reaction process incorporating water and heat recovery is proposed for further optimisation of hydrogen production from steam reforming of glycerol.     

H2 production in silica membrane reactor via methanol steam reforming: Modeling and HAZOP analysis

The main aim of this work is the presentation of both qualitative safety and quantitative operating analyses of silica membrane reactor (MR) for carrying out methanol steam reforming (MSR) reaction to produce hydrogen. To perform the safety analysis, HAZOP method is used. Before the HAZOP analysis, a comprehensive investigation of most important operating parameters effects on silica MR performance is required. Therefore, for a quantitative analysis, a 1-dimensional and isothermal model is developed for evaluating the reaction temperature, reaction pressure, feed molar ratio (steam/methanol) and feed flow rate effects on silica MR performance in terms of methanol conversion and hydrogen recovery. The model validation results show good agreement with experimental data from literature. As a consequence, simulation results indicate that the reaction pressure and feed molar ratio have dual effect on silica MR performance. In particular, it is found that methanol conversion is decreased by increasing the reaction pressure from 1.5 to 4.0 bar, whereas over 4.0 bar, it is improved. Moreover, the hydrogen recovery is decreased by increasing the feed molar ratio from 1 to 5, while over 5, it was approximately constant. After the evaluation of modeling results, the HAZOP analysis for silica MR is carried out during MSR reaction. The analysed operating parameters in the modeling study have been considered as key parameters in the HAZOP analysis. The safety assessment results are presented in tables as check list. By considering the HAZOP results, safety pretreatment works are recommended before or during the experimental tests of MSR reaction in silica MR. According to different parameters consequences, reaction temperature is the most critical parameter in MSR reaction for the silica MR studied in this work. In particular, to avoid the consequences of temperature deviation, it is recommended to use a PID temperature controller in the silica MR for MSR reaction.     

Hydrogen rich gas production by the autothermal reforming of biodiesel (FAME) for utilization in the solid-oxide fuel cells: A thermodynamic analysis

The thermodynamics of the autothermal reforming (ATR) of biodiesel (FAME) for production of hydrogen is simulated and evaluated using Gibbs free minimization method. Simulations are performed with water-biodiesel molar feed ratios (WBFR) between 3 and 12, and oxygen-biodiesel molar feed ratio (O_XBFR) from 0 to 4.8 at reaction temperature between 300 and 800 °C at 1 atm. Yields of H₂ and CO are calculated as functions of WBFR, O_XBFR and temperature at 1 atm. Hydrogen rich gas can be produced by the ATR of biodiesel for utilization in solid-oxide fuel cells (SOFCs). The best operating conditions for the ATR reformer are WBFR≥9 and O_XBFR = 4.8 at 800 °C by optimization of the operating parameters. Yields of hydrogen and carbon monoxide are 68.80% and 91.66% with 54.14% and 39.2% selectivities respectively at the above conditions. The hydrogen yield from biodiesel is higher than from unmodified oils i.e., transesterification increases hydrogen yield. Increase in saturation of the esters, results in increase in methane selectivity, while an increase in unsaturation results in a decrease in methane selectivity. Increase in degree of both saturation and unsaturation of esters, increases coke selectivity. Similarly an increase in the linoleic content of esters, increases coke selectivity.     

Hydrogen by glycerol steam reforming on a nickel–alumina catalyst: Deactivation processes and regeneration

Hydrogen energy has attracted considerable attention because of its efficiency and environmental benefits, and the increasing demand requires finding renewable sources of raw materials to produce it. Glycerol, by-product of biodiesel production and coming from renewable raw materials, could be a bio-renewable substrate to produce hydrogen. The glycerol steam reforming to obtain hydrogen was evaluated using a 5.1 wt% Ni impregnated on Al₂O₃ catalyst, characterized by nitrogen adsorption, XRD, and FTIR. Deactivation processes were analyzed in successive cycles of reaction at 700 °C, atmospheric pressure, 5 h⁻¹ WHSV, and 3:1 water:glycerol molar ratio, during 12 h. Between reaction cycles, regenerating took place using a He/Air stream. Hydrogen was the main product on the fresh catalyst, following by CO and CH₄; during reaction, carbonaceous deposits deactivated catalyst, decreasing H₂ and increasing both CO and CH₄. Carbonaceous deposits were characterized by TPO, showing a main peak centered at 690 °C; the carbon content reached 11.9%.     

Thermodynamic analysis of the autothermal reforming of glycerol using supercritical water

Hydrogen can be produced by autothermal reforming of glycerol using supercritical water (SCW). With the aid of AspenPlus™, a systematic thermodynamic analysis of this process has been carried out by the total Gibbs free energy minimization method, which computes the equilibrium composition of synthesis gas (syngas). The predictive Soave-Redlich-Kwong equation of state (EOS) has been used as thermodynamic method in the simulation of the supercritical region. A sensitivity analysis has been conducted both for a pure glycerol feed and pretreated crude glycerol feed coming from biodiesel production. Simulations run so as to calculate the O₂ needed to enter the Gibbs reactor (reformer) for achieving the thermoneutral condition (no external heat to sustain the reformer operation is required). Thus, the effect of the main operating parameters (reforming temperature, water to glycerol mole ratio, glycerol purity in the feed of crude glycerol, oxygen to glycerol mole ratio and the inlet feed temperature) aimed to the hydrogen production has been investigated, by obtaining the mole fraction and molar flow-rate of components in syngas, as well as the hydrogen yield. By this way, the most thermodynamic favorable operating conditions at which glycerol may be converted into hydrogen by autothermal reforming using SCW have been identified. As a second part of the study, a conceptual design and an energy and exergy analysis of the overall process will be performed later.     

PdCu membrane integration and lifetime in the production of hydrogen from methane

PdCu membranes prepared by sequential electroless plating were integrated into a hydrogen production and purification process. Hydrogen was produced from methane through catalytic partial oxidation and wet catalytic partial oxidation with Ni-based catalysts. Membrane permeance was measured with thermal cycles in an inert and hydrogen atmosphere at 673 and 773 K. Permeability was 1.98·10⁻³ mol/(smPa^0.5) at 673 K and 2.62·10⁻³ mol/(smPa^0.5) at 773 K. The optimum sweep gas flow required in the membrane module when operating with hydrogen-containing mixtures was selected. Peak hydrogen recovery was obtained using 15–20% of the feed to the module as sweep gas flow. Membranes were then placed downstream of the hydrogen production reactor. The CO and H₂O percentages fed to the membrane module did not have a major impact on membrane behavior. Around 60–67% of the hydrogen fed to the membrane module was separated, regardless of its composition.     

Thermodynamic analysis of hydrogen production via glycerol steam reforming with CO2 adsorption

Thermodynamic equilibrium for glycerol steam reforming to hydrogen with carbon dioxide capture was investigated using Gibbs free energy minimization method. Potential advantage of using CaO as CO₂ adsorbent is to generate hydrogen-rich gas without a water gas shift (WGS) reactor for proton exchange membrane fuel cell (PEMFC) application. The optimal operation conditions are at 900 K, the water-to-glycerol molar ratio of 4, the CaO-to-glycerol molar ratio of 10 and atmospheric pressure. Under the optimal conditions, complete glycerol conversion and 96.80% H₂ and 0.73% CO concentration could be achieved with no coke. In addition, reaction conditions for coke-free and coke-formed regions are also discussed in glycerol steam reforming with or without CO₂ separation. Glycerol steam reforming with CO₂ adsorption has the higher energy efficiency than that without adsorption under the same reaction conditions.     

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.     

Robust modelling development for optimisation of hydrogen production from biomass gasification process using bootstrap aggregated neural network

In this study, a robust model using bootstrapped aggregated neural network (BANN) was developed for optimising operating conditions of a two-stage gasification for high carbon conversion, high hydrogen yield and low CO₂. The developed BAAN model predicted accurately (R² of 0.999) the gas composition and the 95% confidence bounds for model predictions on unseen validation data indicated good prediction reliability for various feedstock. The BANN was also used to predict the optimum operating condition for hydrogen production from waste wood (1st stage temperature of 900 °C, 2nd stage temperature of 1000 °C, steam/carbon molar ratio of 5.7) to achieve high hydrogen (71–72 mol%), gas yield (98–99 wt%) and low CO₂ (17–18 mol%). The optimal conditions were tested in the laboratory and the experimental results agreed well with the predicted data with an error of 0.01–0.05. Sensitivity analysis revealed that an increase in temperatures for both stages and high steam/carbon ratio favoured the H₂ production and carbon conversion.     

Theoretical study of hydrogen production by ethanol steam reforming: Technical evaluation and performance analysis of catalytic membrane reactor

Ethanol steam reforming over a Co/Al₂O₃ catalyst was studied theoretically in a catalytic PdAg membrane reactor (CMR). A mathematical model has been developed to elucidate the behavior of CMR by taking into account the chemical reactions, heat and mass transfer phenomena. The effect of operating parameters on the performance of CMR has been evaluated in terms of ethanol conversion, hydrogen recovery and hydrogen yield. The results revealed the high performance of this configuration is related to the continuous removal of hydrogen from the retentate side, shifting the reaction equilibrium towards hydrogen formation. Sensitivity analysis of operating parameters indicate that ethanol conversion is favored at higher temperatures, pressures, sweep ratios and feed molar ratios. Moreover, increasing the feed molar ratio enhances the ethanol conversion, and decreases the hydrogen recovery due to reduction of partial pressure of hydrogen and consequently decreasing the driving force for the hydrogen permeation through the membrane.     

Performance assessment and evaluation of catalytic membrane reactor for pure hydrogen production via steam reforming of methanol

The steam reforming of methanol was investigated in a catalytic Pd–Ag membrane reactor at different operating conditions on a commercial Cu/ZnO/Al₂O₃ catalyst. A comprehensive two-dimensional non-isothermal stationary mathematical model has been developed. The present model takes into account the main chemical reactions, heat and mass transfer phenomena in the membrane reactor with hydrogen permeation across the PdAg membrane in radial direction. Model validation revealed that the predicted results satisfy the experimental data reasonably well under the different operating conditions. Also the impact of different operating parameters including temperature, pressure, sweep ratio and steam ratio on the performance of reactor has been examined in terms of methanol conversion and hydrogen recovery. The modeling results have indicated the high performance of the membrane reactor which is related to continuous removal of hydrogen from retentate side through the membrane to shift the reaction equilibrium towards formation of hydrogen. The obtained results have confirmed that increasing the temperature improves the kinetic properties of the catalyst and increase in the membrane's H₂ permeance, which results in higher methanol conversion and hydrogen production. Also it is inferred that the hydrogen recovery is favored at higher temperature, pressure, sweep ratio and steam ratio. The model prediction revealed that at 573 K, 2 bar and sweep ratio of 1, the maximum hydrogen recovery improves from 64% to 100% with increasing the steam ratio from 1 to 4.     

Hydrogen permeation enhancement in a Pd membrane tube system under various vacuum degrees

Hydrogen purification using palladium (Pd) membrane technology has been seen as a potential solution for producing pure hydrogen form hydrogen-rich gas. Compared to traditional practices of operating the permeate side of the membrane at atmospheric pressure, in this study, a vacuum is applied. The effects of various vacuum degrees applied to the permeate side of the Pd membrane are investigated and compared to the results under normal operation without a vacuum. The feed gas used for experiments consists of a mixture of hydrogen (70 vol%) and nitrogen (30 vol%). Three membrane operating temperatures (320, 350, and 380 °C), four pressure differences (2, 3, 4, and 5 atm) across the membrane, and four vacuum degrees (−15, −30, −45, and −53 kPa) applied to the permeate side are considered. For the three operating temperatures, the best improvements in the performance of hydrogen permeation are at 320 and 350 °C when a −53 kPa vacuum is applied, resulting in 79.4% and 79.1% improvements, respectively, compared to normal operations. Increasing temperatures leads to an increase in H₂ permeation both with and without a vacuum; however, best performances of H₂ permeation are observed in cases without a vacuum.