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.     

An energy and exergy analysis of the supercritical water reforming of glycerol for power production

As a continuation of a previous work, a conceptual design is proposed for reforming glycerol using supercritical water to produce maximum electrical power in an energy self-sufficient system. The scheme of the process is simulated after discussing some routes to achieve the aim. The selected way takes advantage of the huge pressure energy of reformate products just at the outlet of the reforming process. The expanded product gas is used as a fuel gas to provide the thermal energy required by the reforming process. The evaluation of the thermodynamic performance of the process is carried out by an energy and exergy analysis. As relevant outputs measurements of the process performance, the net work and exergetic efficiencies as well as the mole fraction and molar flow-rates of hydrogen obtained. Glycerol feed concentration in aqueous solution at which no external heat source is needed was obtained, both for pure and pretreated crude glycerol, at 800 °C and 240 atm. The effect of the main operating parameters has been investigated by sensitivity analysis to identify optimal conditions that maximize power production. In the exergy analysis, the thermodynamic efficiencies used for the overall process and for its individual units are suitably discussed. The computation has been made with the aid of AspenPlus™, using the predictive Soave-Redlich-Kwong equation of state as thermodynamic method in the simulation of the supercritical region. The next study in this series of glycerol reforming using SCW will aim to maximize hydrogen production, including the syngas purification, to generate electricity via fuel cells.     

Optimization of hydrogen production from three reforming approaches of glycerol via using supercritical water with in situ CO2 separation

A pathway for hydrogen production from supercritical water reforming of glycerol integrated with in situ CO₂ removal was proposed and analyzed. The thermodynamic analysis carried out by the minimizing Gibbs free energy method of three glycerol reforming processes for hydrogen production was investigated in terms of equilibrium compositions and energy consumption using AspenPlus™ simulator. The effect of operating condition, i.e., temperature, pressure, steam to glycerol (S/G) ratio, calcium oxide to glycerol (CaO/G) ratio, air to glycerol (A/G) ratio, and nickel oxide to glycerol (NiO/G) ratio on the hydrogen production was investigated. The optimum operating conditions under maximum H₂ production were predicted at 450 °C (only steam reforming), 400 °C (for autothermal reforming and chemical looping reforming), 240 atm, S/G ratio of 40, CaO/G ratio of 2.5, A/G ratio of 1 (for autothermal reforming), and NiO/G ratio of 1 (for chemical looping reforming). Compared to three reforming processes, the steam reforming obtained the highest hydrogen purity and yield. Moreover, it was found that only autothermal reforming and chemical looping reforming were possible to operate under the thermal self-sufficient condition, which the hydrogen purity of chemical looping reforming (92.14%) was higher than that of autothermal reforming (52.98%). Under both the maximum H₂ production and thermal self-sufficient conditions, the amount of CO was found below 50 ppm for all reforming processes.     

Thermodynamic study on the integrated supercritical water gasification with reforming process for hydrogen production: Effects of operating parameters

In this paper, a conceptual process design of the integrated supercritical water gasification (SCWG) and reforming process for enhancing H₂ production has been developed. The influence of several operating parameters including SCWG temperature, SCWG pressure, reforming temperature, reforming pressure and feed concentration on the syngas composition and process efficiency was investigated. In addition, the thermodynamic equilibrium calculations have been carried out based on Gibbs free energy minimization by using Aspen Plus. The results showed that the higher H₂ production could be obtained at higher SCWG temperature, the H₂ concentration increased from 5.40% at 400 °C to 38.95% at 600 °C. The lower feed concentration was found to be favorable for achieving hydrogen-rich gas. However, pressure of SCWG had insignificant effect on the syngas composition. The addition of reformer to the SCWG system enhanced H₂ yield by converting high methane content in the syngas into H₂. The modified SCWG enhanced the productivity of syngas to 151.12 kg/100kg_feed compared to 120.61 kg/100kg_feed of the conventional SCWG system. Furthermore, H₂ yield and system efficiency increased significantly from 1.81 kg/100kg_feed and 9.18% to 8.91 kg/100kg_feed, and 45.09%, respectively, after the modification.     

Catalytic reforming of glycerol in supercritical water with nickel-based catalysts

The catalytic performance of nickel catalysts supported on La₂O₃, α-Al₂O₃, γ-Al₂O₃, ZrO₂, and YSZ for supercritical water reforming of glycerol was investigated. Experiments were conducted in a tubular reactor made of Inconel-625 with the temperature range of 723–848 K under a pressure of 25 MPa. Carbon formation causing operation failure was observed for α-Al₂O₃, γ-Al₂O₃ and ZrO₂ at temperatures higher than 748, 798 and 823 K, respectively. Ni/La₂O₃ exhibited the highest H₂ yield where almost complete conversion was obtained at 798 K. Moderate space velocities (WHSV = 6.45 h⁻¹) and glycerol feed concentration (5wt.%) favor high hydrogen selectivity and yield. Methanation is favored at a low WHSV or high glycerol feed concentration, resulting in a lower H₂ yield. Increasing Ni loading on the Ni/La₂O₃ catalyst strongly promoted the reforming, water–gas shift, and methanation reactions, which contributed significantly to the product species distribution.     

Hydrogen production from catalytic supercritical water reforming of glycerol with cobalt-based catalysts

Glycerol reforming under catalytic supercritical water at temperatures in the range of 723–848 K using Co catalyst deposited on various supports including ZrO₂, yttria-stabilized zirconia (YSZ), La₂O₃, γ-Al₂O₃, and α-Al₂O₃ was investigated. An increase in operating temperature promoted the continued increase in glycerol conversion; however, carbon formation causing system operation failure was observed for γ-Al₂O₃ and α-Al₂O₃ at high operating temperatures (i.e. 748–798 K). Co supported on YSZ provided the most efficient performance for hydrogen production. 10 wt.% Co loading on YSZ support was an optimum amount to enhance the reaction. The increase in glycerol conversion and reduction of the amount of liquid products were observed for lower weight hourly space velocity (WHSV), higher operating temperature or higher cobalt loading. On Co/YSZ catalyst, glycerol conversion of 0.94 and hydrogen yield of 3.72 was obtained with WHSV of 6.45 h⁻¹at 773 K.     

Hydrogen and power generation from supercritical water reforming of glycerol and pressurized SOFC integrated system: Use of different CO2 adsorption process

The performance analysis of an integrated system of glycerol supercritical water reforming and pressurized SOFC was presented. The use of different CO₂ adsorption processes that include in situ and ex situ processes was compared to determine the suitable process for hydrogen and power generations. The influence of operating condition, e.g., temperature and pressure of reformer, supercritical water to glycerol (S/G) molar ratio, and calcium oxide to glycerol (CaO/G) molar ratio was examined. Then, the electrical performance of each integrated process was considered with respect to the SOFC conditions comprising temperature, pressure, and current density. The simulation results revealed that both processes have same favourable conditions for temperature and pressure operated at 800 °C and 240 atm, respectively. The suitable S/G and CaO/G molar ratios for in situ process are 10 and 2 whereas those for ex situ process are 20 and 1. Under these conditions, maximum hydrogen can be achieved as 87% and 75% for in situ and ex situ processes, respectively. When both integrated processes are operated at the optimal SOFC conditions as 900 °C, 4 atm, and current density of 10,000 A/m², the SOFC efficiency of 71.56% and 62.12% can provide for in situ and ex situ processes, respectively.     

Techno-economic comparison of three biodiesel production scenarios enhanced by glycerol supercritical water reforming process

In this study, techno-economic comparison of three different biodiesel production scenarios integrated with glycerol supercritical water reforming (SCWR) process to produce electricity is conducted. In the first scenario, biodiesel is synthesized from acid-pretreated waste cooking oil (WCO) in the presence of alkali catalyst. In the second scenario, biodiesel is obtained from WCO by acid catalyst. In the third scenario, biodiesel is derived from WCO using acid catalyst, followed by hexane extraction of the produced methyl esters. The glycerol evolved from all the above-mentioned pathways is then subjected to the SCWR process in order to produce hydrogen. The produced hydrogen is then combusted to provide thermal energy required by biodiesel production and purification processes as well as to generate electricity. All the developed scenarios are modeled and simulated in Aspen HYSYS software environment. In order to simplify the simulation process, canola-based WCO is considered as triolein with 6 wt% oleic acid (free fatty acid) and, accordingly, the prepared biodiesel is taken into account as methyl oleate. In order to compare the economic profitability of the developed approaches, several economic indicators including net present value (NPV), internal rate of return (IRR), payback period (PBP), discounted payback period (DPBP), and return on investment (ROI) are used. A sensitivity analysis is also carried out to show how variations in feedstock, biodiesel, and electricity prices can affect the NPV of the developed scenarios. According to the results obtained, the highest IRR and ROI values as decision-making parameters are obtained for the first scenario, manifesting its suitability from the techno-economic viewpoint. The economic indicators of the second scenario are also acceptable and very close to the first approach. Overall, upgrading glycerol into hydrogen using SCWR process appears to be an attractive strategy for enhancing the economic viability of biodiesel production plants.     

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.     

Thermodynamic analysis of hydrogen production from glycerol autothermal reforming

In this work, thermodynamics was applied to investigate the glycerol autothermal reforming to generate hydrogen for fuel cell application. Equilibrium calculations employing the Gibbs free energy minimization were performed in a wide range of temperature (700–1000 K), steam to glycerol ratio (1–12) and oxygen to glycerol ratio (0.0–3.0). Results show that the most favorable conditions for hydrogen production are achieved with the temperatures, steam to glycerol ratios and oxygen to glycerol ratios of 900–1000 K, 9–12 and 0.0–0.4, respectively. Further, it is demonstrated that thermoneutral conditions (steam to glycerol ratio 9–12) can be obtained at oxygen to glycerol ratios of around 0.36 (at 900 K) and 0.38–0.39 (at 1000 K). Under these thermoneutral conditions, the maximum number of moles of hydrogen produced are 5.62 (900 K) and 5.43 (1000 K) with a steam to glycerol ratio of 12. Also, it should be noted that methane and carbon formation can be effectively eliminated.     

Catalytic gasification of glycine and glycerol in supercritical water

Glycine and glycerol were used as the model compounds of protein and fattiness, respectively. A continuous tubular-flow reactor was used for the gasification experiments operated at 380–500 °C and 25 MPa with or without Na₂CO₃ catalyst. Compared with a negative effect on glycerol gasification, Na₂CO₃ could increase hydrogen yield and Chemical Oxygen Demand (COD) destruction efficiency, and the catalytic performance of 0.1 wt% Na₂CO₃ was better than that of 0.2 wt% for glycine gasification. When 1 wt% glycine solution with 0.1 wt% Na₂CO₃, or 1 wt% glycerol solution without Na₂CO₃ was gasified at 500 °C with the residence time of 0.98 min, their corresponding gasification efficiencies were up to 95.8% and 98%, and hydrogen yields could reach 4.14 and 5.08 mol/mol, respectively. Hydrogen molar fraction in gaseous product was about 60% and liquid effluents could be reutilized. Correspondingly, the ideal overall reaction equations for glycine and glycerol gasification were proposed.     

Parametric study on electrochemical reforming of glycerol for hydrogen production

Hydrogen production by electrochemical reforming of glycerol was investigated in this study. Within this scope, the performance of the system under different operating conditions was evaluated by parametric studies and optimum operating conditions were determined. The effects of membrane type, membrane pre-treatment procedure and temperature were investigated. System performance was examined also with long-term tests. The formation of hydrogen at the cathode was determined by analyzing the product gases by gas chromatography. Optimum condition for maximum hydrogen production was obtained with the Zn/Zn electrode pair in the presence of 0.4 M glycerol and 0.04 M H₂SO₄ at the anode side, 0.04 M H₂SO₄ at the cathode side and with pre-treated Nafion XL membrane. As the result of performance tests, room temperature and 2 V potential were found to be the most suitable operating conditions.     

Hydrogen production from glycerol by supercritical water gasification in a continuous flow tubular reactor

In this work, glycerol was used for hydrogen production by supercritical water gasification. Experiments were conducted in a continuous flow tubular reactor at 445∼600 °C, 25 MPa, with a short residence time of 3.9∼9.0 s. The effects of reaction temperature, residence time, glycerol concentration and alkali catalysts on gasification were systematically studied. The results showed that the gasification efficiency increased sharply with increasing temperature above 487 °C. A short residence time of 7.0 s was enough for 10 wt% glycerol gasification at 567 °C. With the increase of glycerol concentration from 10 to 50 wt%, the gasification efficiency decreased from 88% to 71% at 567 °C. The alkali catalysts greatly enhanced water-gas shift reaction and the hydrogen yield in relation to catalysts was in the following order: NaOH > Na₂CO₃>KOH > K₂CO₃. The hydrogen yield of 4.93 mol/mol was achieved at 526 °C with 0.1 wt% NaOH. No char or tar was observed in all experiments. The apparent activation energy and apparent pre-exponential factor for glycerol carbon gasification were obtained by assuming pseudo first-order kinetics.     

Thermodynamic evaluation of hydrazine assisted glycerol reforming for syngas production and coke inhibition

Thermodynamic investigation of glycerol reforming has been performed to study hydrogen production, carbon dioxide evolution and coke formation. Gibb's free energy direct minimization procedure was used to calculate the concentration of different components at equilibrium. The analysis was performed at temperatures from 300K to 1000K under unit atmospheric pressure. A comparative study on steam reforming of glycerol (SRG) and glycerol reforming reaction with hydrazine has been conducted in the presence of hydrazine that act as a suitable reducing agent. Incorporation of hydrazine into glycerol reforming system helped in minimizing coke formation, maximizing hydrogen and syn-gas production. A complete conversion of glycerol with coke free products, along with reduced level of carbon dioxide and maximum hydrogen generation was obtained when glycerol steam reforming process (S/G = 1) was combined with higher moles of hydrazine. Reformation at higher temperatures could enhance the hydrogen production and decrease carbon generation due to methanation reaction and hence optimum results were accomplished at 1000K and atmospheric pressure.     

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 study of hydrogen production from crude glycerol autothermal reforming for fuel cell applications

This study presents a thermodynamic analysis of hydrogen production from an autothermal reforming of crude glycerol derived from a biodiesel production process. As a composition of crude glycerol depends on feedstock and processes used in biodiesel production, a mixture of glycerol and methanol, major components in crude glycerol, at different ratios was used to investigate its effect on the autothermal reforming process. Equilibrium compositions of reforming gas obtained were determined as a function of temperature, steam to crude glycerol ratio, and oxygen to crude glycerol ratio. The results showed that at isothermal condition, raising operating temperature increases hydrogen yield, whereas increasing steam to crude glycerol and oxygen to crude glycerol ratios causes a reduction of hydrogen concentration. However, high temperature operation also promotes CO formation which would hinder the performance of low-temperature fuel cells. The steam to crude glycerol ratio is a key factor to reduce the extent of CO but a dilution effect of steam should be considered if reforming gas is fed to fuel cells. An increase in the ratio of glycerol to methanol in crude glycerol can increase the amount of hydrogen produced. In addition, an optimal operating condition of glycerol autothermal reforming at a thermoneutral condition that no external heat to sustain the reformer operation is required, was investigated.     

Hydrogen and/or syngas from steam reforming of glycerol. Study of platinum catalysts

In the present work, Pt catalysts prepared on different supports were evaluated in order to apply them in the steam reforming of glycerol reaction to obtain hydrogen and/or synthesis gas at temperatures lower than 450 °C. A strong support effect on the behavior of catalysts was determined.     

Thermochemical recuperation by ethanol steam reforming: Thermodynamic analysis and heat balance

This article considers the scheme of fuel-consuming equipment with a thermochemical heat recuperation system by using ethanol steam reforming. The main concept of thermochemical recuperation (TCR) is the transformation of exhaust gases heat into chemical energy of a new synthetic fuel that has higher calorimetric properties such as low-heating value. Thermochemical recuperation can be considered as an on-board hydrogen production technology. To determine the efficiency of the thermochemical recuperation system, the thermodynamic analysis via Gibbs free energy minimization method was performed. The software Aspen-HYSYS was used for the thermodynamic analysis. The heat flows were calculated for a wide temperature range from 500 to 1000 K, for steam-to-ethanol ratio from 1 to 3, and for various pressures of 1, 5 and 10 bar. The results of the thermodynamic analysis were compared with the experimental results and the results of the thermodynamic analysis performed by other authors. All obtained results are in a good correlation. In the first law energy analysis was found that for a high steam-to-ethanol ratio (above 3), to perform thermochemical recuperation an external heat must be supplied to the TCR system. The heat deficit for steam-to-ethanol ratio 3 is from 1 to 2 MJ/kg_EtOH in the temperature range from 500 to 1000 K.     

Hydrogen production from glycerol steam reforming for low- and high-temperature PEMFCs

This paper presents a thermodynamic study of a glycerol steam reforming process, with the aim of determining the optimal hydrogen production conditions for low- and high-temperature proton exchange membrane fuel cells (LT-PEMFCs and HT-PEMFCs). The results show that for LT-PEMFCs, the optimal temperature and steam to glycerol molar ratio of the glycerol reforming process (consisting of a steam reformer and a water gas shift reactor) are 1000 K and 6, respectively; under these conditions, the maximum hydrogen yield was obtained. Increasing the steam to glycerol ratio over its optimal value insignificantly enhanced the performance of the fuel processor. For HT-PEMFCs, to keep the CO content of the reformate gas within a desired range, the steam reformer can be operated at lower temperatures; however, a high steam to glycerol ratio is required. This requirement results in an increase in the energy consumption for steam generation. To determine the optimal conditions of glycerol steam reforming for HT-PEMFC, both the hydrogen yield and energy requirements were taken into consideration. The operational boundary of the glycerol steam reformer was also explored as a basic tool to design the reforming process for HT-PEMFC.     

Supercritical water synthesized Ni/ZrO2 catalyst for hydrogen production from supercritical water gasification of glycerol

Catalysts are crucial to promote the technical feasibility of supercritical water gasification (SCWG) for H₂ production from wet biomass, yet catalysts prepared by conventional methods normally encounter sintering problems in supercritical water. Herein, a series of ZrO₂-supported Ni catalysts were tried to be prepared by supercritical water synthesis (SCWS) and evaluated for SCWG in terms of activity and property stability. The SCWS was conducted at 500 °C and 23 MPa using metal nitrates as starting materials. Effect of precursor concentration on property and catalytic performance of the SCWS-prepared catalysts for SCWG of 20 wt% glycerol were systematically studied. XRD, SEM-EDS, TEM and TGA were applied for catalyst characterization. Results verified the successful obtaining of Ni/ZrO₂ nanocatalysts with Ni crystals of 30–70 nm and ZrO₂ crystals of ~11 nm by the SCWS process, which were found to be active on the WGSR for SCWG to increase the H₂ yield as high as 155%. Importantly, the SCWS-prepared Ni/ZrO₂ catalysts exhibited excellent property stability and anti-coking ability for SCWG of glycerol.