Thermodynamic analysis of steam reforming of ethanol and glycerine for hydrogen production

In the past few years there has been a growing interest in environmentally clean renewable sources for hydrogen production. In this context new technologies have been developed for ethanol and glycerine reforming. Hydrogen production varies significantly according to the operating conditions such as pressure, temperature and feed reactants ratio. The thermodynamic analysis provides important knowledge about the effects of those variables on the process of ethanol and glycerine reforming. The present work was aimed at analyzing the thermodynamic steam reforming of ethanol and glycerine, using Gibbs free energy minimization using actual temperature and pressure data found in the literature. The nonlinear programming model was implemented in GAMS^® and the CONOPT2 solver was used to solve the equations. The ideality in gaseous phase and the formation of solid carbon was considered. The methodology used reproduced the most relevant papers involving experimental studies and thermodynamic analysis.     

Optimization of bio-oil steam reforming process by thermodynamic analysis

A straightforward thermodynamic analysis of bio-oil steam reforming was carried out in the context of hydrogen and syngas production, employing Gibbs energy minimization method to determine equilibrium composition and global reaction heat. The bio-oil model compound was a mixture of acetic acid, phenol, and acetone. The effects of process variables, such as temperature and inlet S/C molar ratio, were investigated over a wide range of conditions. Thermodynamic analysis was performed using the software Aspen Plus v.11. It was identified the best operational conditions that could maximize syngas and further hydrogen production considering energy efficiency. The optimum production of hydrogen is 2.28 mol per carbon mole at S/C = 10 and 850 K, and syngas is 2.37 mol per carbon mole at S/C = 10 and 900 K. It has been demonstrated that the equilibrium calculations can be used to simulate these steam reforming reactions, given the catalyst's behavior.     

Thermodynamic equilibrium analysis of combined carbon dioxide reforming with steam reforming of methane to synthesis gas

Thermodynamics equilibrium analysis of carbon dioxide reforming of methane combined with steam reforming to synthesis gas was studied by Gibbs free energy minimization method to understand the effects of process variables such as temperature, pressure and inlet CH₄/H₂O/CO₂ ratios on product distributions. For this purpose, the calculations were carried out at total pressures of 1 and 20 bar, and at ranges of temperature and steam-to-carbon ratios of 200–1200 °C and 0–0.50, respectively. The results revealed that carbon dioxide reforming of methane combined with steam reforming process was controlled by different reactions with regard to the operating temperature, pressure and varying feed compositions. The H₂/CO product ratio could be modified by changing the relative concentration of steam and CO₂ in the feed, temperature and pressure, depending on the downstream application.     

Hydrogen production via sorption enhanced steam reforming of butanol: Thermodynamic analysis

Thermodynamic equilibrium for sorption enhanced steam reforming of butanol (SESRB) to hydrogen was investigated using Gibbs free energy minimization method. The optimal operation conditions for SESRB are at 800 K, the steam-to-butanol molar ratio of 10, the calcium oxide-to-butanol molar ratio of 8 and atmospheric pressure. Under the optimal conditions, complete conversion of butanol, 97.07% concentration of H₂ and 0.05% concentration of CO₂, and efficiency of 86.60% could be achieved and at which no coke tends to form. Under the same conditions in SRB, 58.18% concentration of H₂, 21.62% concentration of CO₂, and energy efficiency of 81.51% could be achieved. Butanol steam reforming with CO₂ adsorption has the higher H₂ content and efficiency, and lower CO₂ content than that without adsorption under the same reaction conditions. In addition, reaction conditions for coke-free and coke-formed regions are also discussed in butanol steam reforming with or without CO₂ separation.     

Energy analysis of ethanol steam reforming for hybrid electric vehicle

Thermodynamic equilibrium of ethanol steam reforming is studied using the Gibbs free energy minimization method. The reaction paths of ethanol steam reforming are simulated using Chem‐CAD software. Appropriate optimization of reactants ratio and reaction conditions is performed, to achieve the composition of ethanol steam reforming products, which will be favorable as an internal combustion engine (ICE) fuel. The effects of process variables, such as temperature and water : ethanol molar ratio are discussed. Numerical investigations are conducted to analyze energy performance of steam reforming of ethanol for ICE. Realization of ethanol steam reforming at high temperature leads to an increase in efficiency of the process. The optimal conditions are obtained as follows: 1100 K, water : ethanol molar ratio of 1.2. Copyright © 2011 John Wiley & Sons, Ltd.     

Optimization of two bio-oil steam reforming processes for hydrogen production based on thermodynamic analysis

Thermodynamics of hydrogen production from conventional steam reforming (C-SR) and sorption-enhanced steam reforming (SE-SR) of bio-oil was performed under different conditions including reforming temperature, S/C ratio (the mole ratio of steam to carbon in the bio-oil), operating pressure and CaO/C ratio (the mole ratio of CaO to carbon in the bio-oil). Increasing temperature and S/C ratio, and decreasing the operating pressure were favorable to improve the hydrogen yield. Compared to C-SR, SE-SR had the significant advantage of higher hydrogen yield at lower desirable temperature, and showed a significant suppression for carbon formation. However excess CaO (CaO/C > 1) almost had no additional contribution to hydrogen production. Aimed to achieve the maximum utilization of bio-oil with as little energy consumption as possible, the influences of temperature and S/C ratio on the reforming performance (energy requirements and bio-oil consumption per unit volume of hydrogen produced, Q_D/H2 (kJ/Nm³) and Y_Bio-oil/H2 (kg/Nm³)) were comprehensively evaluated using matrix analysis while ensuring the highest hydrogen yield as possible. The optimal operating parameters were confirmed at 650 °C, S/C = 2 for C-SR; and 550 °C, S/C = 2 for SE-SR. Under their respective optimal conditions, the Y_Bio-oil/H2 of SE-SR is significant decreased, by 18.50% compared to that of C-SR, although the Q_D/H2 was slightly increased, just by 7.55%.     

Properties of thermodynamic equilibrium-based methane autothermal reforming to generate hydrogen

The characteristics of methane autothermal reforming to generate hydrogen were studied with thermodynamic equilibrium constant method. Results show that the methane steam reforming reaction is prone to backward at low temperature, and there is an inflection point temperature that the reaction turns forward. When steam–methane molar ratio is 2, the inflection point temperature increases with raising air–methane molar ratio. When air–methane molar ratio is 1, the inflection point temperature maintains between 700 and 800 K. Hydrogen yield increases firstly and then decreases with elevated temperature. The increase of air–methane molar ratio leads to a lower hydrogen production when temperature exceeds 1000 K. Increasing steam–methane molar ratio promotes the hydrogen production. Methane autothermal reforming occurs much more easily when temperature keeps at 1000 K and the molar ratio of air–methane and steam–methane is 1 and 2 respectively. Changing the steam–methane molar ratio can regulate H₂/CO molar ratio.     

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.     

Exergy analysis of hydrogen production via steam methane reforming

The performance of hydrogen production via steam methane reforming (SMR) is evaluated using exergy analysis, with emphasis on exergy flows, destruction, waste, and efficiencies. A steam methane reformer model was developed using a chemical equilibrium model with detailed heat integration. A base-case system was evaluated using operating parameters from published literature. Reformer operating parameters were varied to illustrate their influence on system performance. The calculated thermal and exergy efficiencies of the base-case system are lower than those reported in literature. The majority of the exergy destruction occurs due to the high irreversibility of chemical reactions and heat transfer. A significant amount of exergy is wasted in the exhaust stream. The variation of reformer operating parameters illustrated an inverse relationship between hydrogen yield and the amount of methane required by the system. The results of this investigation demonstrate the utility of exergy analysis and provide guidance for where research and development in hydrogen production via SMR should be focused.     

Comparative study of fuel gas production for SOFC from steam and supercritical-water reforming of bioethanol

Theoretical study of fuel gas (H₂ + CO) production for SOFC from bioethanol was carried out to compare performances between two reforming technologies, including steam reforming (SR) and supercritical-water reforming (SCWR). It demonstrates that the fuel gas productions are comparable among the two reforming systems; however, SCWR requires the operation at much higher temperature and pressure than SR. The maximum hydrogen yield can be obtained at 850 K, atmospheric pressure, ethanol to water molar feed ratio of 1:20 for SR system and at 1300 K, 22.1 MPa, and ethanol to water feed ratio of 1:20 for SCWR. The use of a distillation column to purify the bioethanol feed was proven to improve the fuel conversion efficiency of both systems. The analysis reveals that SCWR is a promising system for fuel production for SOFC when a gas turbine is incorporated to the system for energy recovery. Further, it is not necessary to distil bioethanol to obtain too high ethanol recovery (i.e. >90%) as higher energy consumption at the distillation column could lead to lower overall thermal efficiency.     

Novel structured catalysts configuration for intensification of steam reforming of methane

Structured catalysts, using highly conductive carriers, can improve the heat transfer along the catalytic bed, affording high performance with a flattened radial temperature gradient. The effect of thermal conductivity of structured carriers on highly endothermic Steam Reforming reaction is investigated. The performance of the structured catalysts, obtained on Cordierite and Silicon Carbide (SiC) monoliths, demonstrates the direct correlation between the thermal conductivity of the carrier, the methane conversion and the hydrogen productivity. The evaluation of the monolith configuration shows that the SiC “wall flow” guarantees a better axial and radial thermal distribution, with respect to the SiC “flow through”, resulting in better catalytic activity up to a temperature reaction of 750 °C. The comparison among the performance of the structured catalysts and the commercial 57-4MQ, provided by Katalco-JM, highlights the choice of structured catalysts, which require a lower temperature outside of the reactor, increasing the process efficiency.     

Gibbs free energy minimization as a way to optimize the combined steam and carbon dioxide reforming of methane

Gibbs free energy minimization was applied to study thermodynamic equilibrium of the combined steam and carbon dioxide reforming of methane. Coke deposition, the content of methane and carbon dioxide in syn-gas as well as H₂/CO ratio were investigated as a function of CO₂/CH₄ and H₂O/CH₄ mole ratios at different temperatures and pressures. The ranges of the molar ratios CH₄/CO₂/H₂O in the feed with H₂/CO = 2.1-2.2 were identified at which reforming of methane is not complicated by coke deposition. For each range optimized CH₄/CO₂/H₂O molar ratios characterized by the lowest content of methane and carbon dioxide in syn-gas were found.     

Thermodynamic analysis of propane dry and steam reforming for synthesis gas or hydrogen production

Thermodynamics was applied to investigate propane dry reforming (DR) and steam reforming (SR). Equilibrium calculations employing the Gibbs free energy minimization were performed upon a wide range of pressure (1–5 atm), temperature (700–1100 K), carbon dioxide to propane ratio (CPR, 1–12) and water to propane ratio (WPR, 1–18). From a thermodynamic perspective, it is demonstrated that DR is promising for production of synthesis gas with low hydrogen content, as opposite to SR which favours generation of synthesis gas with high hydrogen content. Complete conversion of propane was obtained for the range of pressure, temperature, CPR and WPR considered in this study. Atmospheric pressure is shown to be preferable for both DR and SR. Approximately 10 mol of synthesis gas can be produced per mole of propane at a temperature greater than 1000 K from DR when CPR is higher than 6. The optimum conditions for synthesis gas production from DR are found to be 975 K (CPR = 3) for a H₂/CO ratio of 1 and 1100 K (CPR = 1) for a H₂/CO ratio of 2. The greatest CO₂ conversion (95%) can be obtained also at 1100 K and CPR = 1. Preferential conditions for hydrogen production from SR are achieved with the temperatures between 925 and 975 K and WPRs of 12–18. The maximum number of moles of hydrogen produced is 9.1 (925 K and WPR = 18). Under conditions that favour hydrogen production, methane and carbon formation can be eliminated to negligible level.     

Comparative exergy analysis of sorption enhanced and conventional methane steam reforming

Exergy efficiency analysis tool is used to evaluate sorption enhanced steam reforming in comparison with the industrial hydrogen production route, steam reforming. The study focuses on hydrogen production for use in high pressure processes. Thermodynamic sensitivity analysis (effect of reforming temperature on hydrogen yield and reforming enthalpy) was performed to indicate the optimum temperature (650 °C) for the sorption enhanced reforming. The pressure was selected to be, for both cases, 25 bar, a typical pressure used in the industrial (conventional) process. Atmospheric pressure, 1000 °C and CO₂ as inert gas were specified as the optimum operating parameters for the regeneration of the sorbent after performing exergy efficiency analysis of three realistic case scenarios. Aspen Plus simulation process schemes were built for conventional and sorption enhanced steam reforming processes to attain the mass and energy balances required to assess comparatively exergy analysis. Simulation results showed that sorption enhanced reforming can lead to a hydrogen purity increase by 17.3%, along with the recovery of pure and sequestration-ready carbon dioxide. The exergy benefit of sorption enhanced reforming was calculated equal to 3.2%. Analysis was extended by adding a CO₂ separation stage in conventional reforming to reach the hydrogen purity of sorption enhanced reforming and enable a more effective exergy efficiency comparison. Following that analysis, sorption enhanced reforming gained 10.8% in exergy efficiency.     

Thermodynamic equilibrium analysis of combined dry and steam reforming of propane for thermochemical waste-heat recuperation

The thermochemical waste-heat recuperation is one for perspective way of increasing the energy efficiency of the fuel-consuming equipment. In this paper, the thermochemical waste-heat recuperation (TCR) by combined steam-dry propane reforming is described. To understand the influence of technological parameter such as temperature and composition of inlet gas mixture on TCR efficiency, thermodynamic equilibrium analysis of combined steam-dry propane reforming was investigated by Gibbs free energy minimization method upon a wide range of temperature (600–1200 K) and different feed compositions at atmospheric pressure. The carbon and methane formation was also calculated and shown. From a thermodynamic perspective, the TCR can be used for increasing energy efficiency at temperatures above 950 K because in this range the maximum conversion rate is reached (from 1.22 to 1.30 for the different feed composition). Approximately 10 mol of synthesis gas can be generated per mole of propane at the temperatures greater than 1000 K. Furthermore, the propane conversion rate and yield of hydrogen are increased with the addition of extra steam to the feed stock. Also, undesirable carbon formation can be eliminated by adding steam to the feed. The thermodynamic equilibrium analysis was accomplished by IVTANTHERMO which is a process simulator for thermodynamic modeling of complex chemically reacting systems and several results were checked by Aspen-HYSYS.     

Thermodynamic analysis of steam reforming of ethanol for hydrogen generation

Thermodynamic equilibrium of ethanol steam reforming has been studied by Gibbs free energy minimization method for hydrogen production in the ranges of water‐to‐ethanol ratio from 0 to 20, reaction temperature from 400 to 2000 K, pressure from 1 to 60 atm, argon‐to‐ethanol ratio from 0 to 100. The optimal conditions suitable for the use in molten carbonate fuel cell and solid oxide fuel cell were obtained as follows: 900–1200 K, water‐to‐ethanol ratio of 3:6, and 1 atm. Under the optimal conditions, complete conversion of ethanol, 60.52–83.58% yield of hydrogen and 32.82–79.60% yield of carbon monoxide could be obtained and no coke forms. Higher pressures have a negative effect, but inert gases have a positive effect, on the hydrogen yield. Coke tends to form at lower temperatures and lower water‐to‐ethanol ratios. Copyright © 2008 John Wiley & Sons, Ltd.     

Improvement of steam methane reforming via in-situ CO2 sorption over a nickel-calcium composite catalyst

Optimization of steam methane reforming (SMR) reaction by CO₂ sorption enhancement was investigated. In this study, the sorption-enhanced steam methane reforming reaction (SESMR) was conducted to maximize hydrogen production via suitable adjustments in the operating conditions of the reaction, which include the molar ratio of steam to CH₄, space velocity, and temperature. The reforming catalysts were prepared by a physical mixture of 20 wt% Ni/Al₂O₃ and CaO. The results reveal that there are significant differences in CH₄ conversion between the SMR and the SESMR from 18% to 108%; this conversion strongly depended on the reaction conditions. High-purity H₂ products (98.9%) with <0.1 ppmv CO were obtained by SESMR under the suitable conditions of 2600 cm³/g/h, steam/CH₄ molar ratio of 4 and 823 K. This implies that the high-quality H₂ produced through the SESMR process could be directly used for the proton-exchange membrane fuel cell.     

Comparison study of thermochemical waste-heat recuperation by steam reforming of liquid biofuels

The concept of thermochemical exhaust heat recuperation by steam reforming of biofuels is considered. Thermochemical recuperation can be considered as an on-board hydrogen production technology. A schematic diagram of a fuel-consuming equipment with thermochemical heat recuperation is described. The thermodynamic analysis of the thermochemical recuperation systems was performed to determine the efficiency of using various fuels, in particular, methanol, ethanol, n-butanol, and glycerol. The thermodynamic analysis was performed by Gibbs free energy minimization method and implemented using the Aspen Hysys program. The thermodynamic analysis was performed for a wide temperature range from 400 to 900 K, for steam-to-fuel of 1, and pressures of 1 bar. The maximum fuel conversion reaches for the following temperatures: methanol - 600 K, ethanol - 730 K, n-butanol - 860 K, glycerol - 890 K. The dependence of the reforming enthalpy on temperature is determined. It was shown that the reaction enthalpy determines the heat transformation coefficient, which shows the ratio of the low heat value of synthetic fuel and the low heat value of the initial fuel. For all studied fuels, the maximum value of the transformation coefficient is observed for steam reforming of ethanol and the maximum heat transformation coefficient is 1.187. The temperature range is determined at which the maximum efficiency of the use of thermochemical recuperation occurs due to the reforming of biofuels. For methanol, the effective temperature is about 600 K, for ethanol is about 700 K, for n-butanol is 850 K, for glycerol is more than 900 K. The results obtained make it possible to efficiently select the type of fuel for thermochemical recuperation due to steam reforming.     

Solar-driven novel methane reforming with carbon looping for hydrogen production

As a renewable source, solar energy plays an important role in meeting energy demand for human beings and in relieving global warming. In this paper, the concentrated solar heat is utilized to drive the high-endothermic methane reforming with carbon looping. In so doing, the process increases the utilization of CO₂ and reduces the carbon emissions as well as saves the extra fuel consumption for combustion, leading to high efficiency of energy utilization. By optimizing this proposed system, the energy efficiency can reach approximate 67.13% with simultaneously reducing CO₂ emissions by 34.98% compared with SMR process. Exergy analysis is used to assess the location of irreversibility within process. The maximal part of exergy destroyer was localized in reformer with a contribution of 68%. In addition, the effects of hourly variation of direct normal irradiation on thermodynamic performance and methane conversion on the four typical days (spring equinox, summer solstice, autumn equinox, winter solstice) were analyzed in this work. The current work might be insightful for solar-hydrogen production field.