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.     

How to choose endothermic process for thermochemical waste-heat recuperation?

The thermochemical waste-heat recuperation (TCR) systems by steam reforming of various hydrocarbon fuels are considered. A method for determining the TCR systems efficiency is proposed. The methodology is based on the determination of the heat recuperation rate and heat transformation coefficient. TCR due to steam reforming of methanol, ethanol, glycerol, propane, and methane was analyzed. To obtain the initial data for energy analysis of TCR systems, the thermodynamic analysis was performed. With the help of Aspen HYSYS was determined the synthesis gas composition and reaction enthalpy for all investigated variants. The investigation was performed for a wide temperature range from 400 to 1200 K, for the steam-to-fuel ratio of 1, and pressures of 1 bar. It was established that TCR due to the steam reforming of ethanol, glycerol, and propane in the temperature range above 800 K, it is possible to achieve complete recuperation of the exhaust after the furnace. As a results of investigation, the practical recommendations were given for choosing endothermic reaction for the thermochemical waste-heat recuperation systems: in the temperature range up to 600 K for TCR it is necessary to choose a methanol steam reforming reaction; in the temperature range from 600 to 1000 K - the reaction of steam reforming of ethanol and glycerol; in the temperature range above 1000 K - the reaction of steam reforming propane and methane.     

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.     

Thermochemical waste‐heat recuperation by steam methane reforming with flue gas addition

The process flow schematic of fuel‐consuming equipment with thermochemical waste‐heat recuperation by steam methane reforming with an addition of flue gas to the reaction mixture is suggested. The advantages of such a thermochemical recuperation (TCR) system compared with the TCR system by steam methane reforming are shown and justified. Based on the first law energy analysis, the heat inputs and outputs of the TCR system were determined. To determine the exhaust gases heat transformed into chemical energy of a new synthetic fuel, the thermodynamic analysis by minimizing Gibbs energy via Aspen HYSYS was performed. It was found that with an increase in the mole fraction of combustion products in the reaction mixture, the enthalpy of the methane reforming reaction increases, especially noticeable at the temperature range above 1000 K. Based on the heat, balance of the TCR system was established that the addition of combustion products to the reaction mixture has the following effects: reducing the heat input for steam production in a steam generator; reduction of the steam generator size because of the need to produce a smaller amount of steam in comparison with TCR by pure steam methane reforming; and reducing the amount of heat transferred through the wall of the reformer and, as a consequence, reduction in size of the reformer.     

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 high‐temperature helium heated fuel reforming for hydrogen production

In order to take full advantage of the heat from high temperature gas cooled reactor, thermodynamic analysis of high‐temperature helium heated methane, ethanol and methanol steam reforming for hydrogen production based on the Gibbs principle of minimum free energy has been carried out using the software of Aspen Plus. Effects of the reaction temperature, pressure and water/carbon molar ratio on the process are evaluated. Results show that the effect of the pressure on methane reforming is small when the reaction temperature is over 900 °C. Methane/CO conversion and hydrogen production rate increase with the water/carbon molar ratio. However the thermal efficiency increases first to the maximum value of 61% and then decreases gradually. As to ethanol and methanol steam reforming, thermal efficiency is higher at lower reaction pressures. With an increase in water–carbon molar ratio, hydrogen production rate increases, but thermal efficiency decreases. Both of them increase with the reaction temperature first to the highest values and then decrease slowly. At optimum operation conditions, the conversion of both ethanol and methanol approaches 100%. For the ethanol and methanol reforming, their highest hydrogen production rate reaches, respectively, 88.69% and 99.39%, and their highest thermal efficiency approaches, respectively, 58.58% and 89.17%. With the gradient utilization of the high temperature helium heat, the overall heat efficiency of the system can reach 70.85% which is the highest in all existing system designs. Copyright © 2014 John Wiley & Sons, Ltd.     

Performance enhancement of methanol reforming reactor through finned surfaces and diffused entry for on-board hydrogen generation

Hydrogen-rich combustion in engines helps in reducing pollutants significantly. But hydrogen usage on a moving vehicle is not getting large-scale user acceptance mainly due to its poor energy storage density resulting in shorter driving ranges. This storage issue led to the hunt for mediums that can efficiently produce on-board hydrogen. Methanol proves to be an efficient alcohol fuel for producing hydrogen through steam reforming reaction. The heat energy required for such endothermic reaction is obtained through exhaust engine waste energy and this process is collectively known as thermochemical recuperation. However, the conventional reactor used for this process faces a lot of problems in terms of efficiency and methanol conversion. In this study, an attempt has been made to improve the design of the reactor for on-board hydrogen generation using engine exhaust heat for addressing the challenges related to performance and hydrogen yield. For enhancing the heat transfer, a finned surface (straight & wavy) was introduced in the reactor which resulted in an increment in methanol conversion significantly. It was found that wavy fin improved the methanol conversion up to 96.8% at an exhaust inlet temperature of 673 K. Also, a diffusing inlet section was introduced to increase the residence time of reactant gases while passing through the catalyst zone. Under given inlet conditions, the methanol conversion for 6° diffuse inlet reactor goes up to 87.9% as compared to 75.4% for the conventional reactor.     

Performance evaluation of a combined power generation system integrated with thermochemical exhaust heat recuperation based on steam methane reforming

The present paper applies the thermodynamic analysis with the determining the efficiency of a combined cycle power plant with a chemically recuperated gas turbine. Thermochemical recuperation of exhaust heat after a gas turbine is realized via the steam methane reforming process. The main concept of combined cycle power plant (CCPP) with chemically recuperated gas turbine (CRGT) is based on the use of exhaust heat for endothermic reforming of the original hydrocarbon fuel in a reformer and for steam generation for a steam cycle. To understand the effect of operating variables such as temperature, pressure, and steam-to-methane ratio on the overall efficiency, the energy and mass balances were compiled. The energy flows were represented by a Sankey diagram. The results of the thermodynamic analysis show that efficiency of CCPP with CRGT is significantly higher (4–7%) than efficiency of CCPP with a conventional gas turbine without TCR. Maximum efficiency of CCPP with CRGT of 0.6412 is observed at inlet temperature of working gas of 1600 °C, pressure of 23 bar for a steam-to-methane ratio of 3.0. In the temperature of inlet working gas below 1200 °C the increase in the efficiency of CCPP with TCR is less than 2%.     

Reforming of methanol to produce hydrogen over the Au/ZnO catalyst

Gold particle with an average size of d_Au ~ 4 nm was dispersed on ZnO by the deposition precipitation method. The fabricated Au/ZnO catalyst was used to produce hydrogen from reforming of methanol. Four reforming reactions, i.e., decomposition of methanol (DM), steam reforming of methanol (SRM), partial oxidation of methanol (POM) and oxidative steam reforming of methanol (OSRM), were evaluated in a fixed bed reactor. A reaction temperature of T_R > 623 K was required for catalyzing reactions of DM and SRM. Interestingly, high methanol conversion (C_MeOH > 90%) was found from reforming reactions of POM and OSRM at an amazing low temperature of T_R < 473 K. Besides, a presentable hydrogen yield (R_H2 ~ 2.4) and a low selectivity of CO (S_CO ~ 1%) were simultaneously attained from the reaction of OSRM. Therefore, the low temperature OSRM reaction over the Au/ZnO catalyst is suggested as a friendly reforming process for on-board production of hydrogen.     

Forging furnace with thermochemical waste-heat recuperation by natural gas reforming: Fuel saving and heat balance

This paper considers thermochemical recuperation (TCR) of waste-heat using natural gas reforming by steam and combustion products. Combustion products contain steam (H₂O), carbon dioxide (CO₂), and ballast nitrogen (N₂). Because endothermic chemical reactions take place, methane steam-dry reforming creates new synthetic fuel that contains valuable combustion components: hydrogen (H₂), carbon monoxide (CO), and unreformed methane (CH₄). There are several advantages to performing TCR in the industrial furnaces: high energy efficiency, high regeneration rate (rate of waste-heat recovery), and low emission of greenhouse gases (CO₂, NO_x). As will be shown, the use of TCR is significantly increasing the efficiency of industrial furnaces – it has been observed that TCR is capable of reducing fuel consumption by nearly 25%. Additionally, increased energy efficiency has a beneficial effect on the environment as it leads to a reduction in greenhouse gas emissions.     

Effect of the vacancy close to heat exchange wall on the heat transfer performance of the solid particles steam generator using waste heat in a methanol steam reforming hydrogen production system

With the massive consumption of fossil fuels and it resulted in significant carbon emissions, it is urgent to find an alternative clean energy source. Hydrogen has been regarded as one of the most promising energy candidates for the next generation. It is a great approach that methane steam reforming for hydrogen production by rational utilization of industrial waste heat, which significantly minimizes carbon emissions and develops methanol steam reforming technology. A solid particle steam generator based on the primary heat exchange method has been proposed, which can provide the heat and steam in the methanol steam reforming hydrogen production system. The quasi-two-dimensional packing heat transfer model of solid particles steam generator was set up.The effect of distance change between the vacancy and the cold wall and distance change between vacancies on heat transfer performance of the steam generator and hydrogen production capacity were studied. As the distance between the vacancy and the wall increases, the heat transfer performance of the steam generator gradually deteriorates, so the steam production of the steam generator decreases, and the system's hydrogen production capacity is reduced, the maximum of the heat flux and the minimum of the apparent thermal resistance are 34.67 kW/m² and 12.02 K/W, respectively. As the distance between vacancies increases, the heat transfer performance of the steam generator is gradually optimized slightly. To maintain the hydrogen production capacity, vacancies should be avoided to appear 2 layers of particles away from the heat exchange wall in the particles steam generator. From the results of the study, the farther the distance between vacancies, the better the steam production and hydrogen production capacity.     

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

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

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.     

Simulation of steam reforming of biogas in an industrial reformer for hydrogen production

The paper aims to investigate the steam reforming of biogas in an industrial-scale reformer for hydrogen production. A non-isothermal one dimensional reactor model has been constituted by using mass, momentum and energy balances. The model equations have been solved using MATLAB software. The developed model has been validated with the available modeling studies on industrial steam reforming of methane as well as with the those on lab-scale steam reforming of biogas. It demonstrates excellent agreement with them. Effect of change in biogas compositions on the performance of industrial steam reformer has been investigated in terms of methane conversion, yields of hydrogen and carbon monoxide, product gas compositions, reactor temperature and total pressure. For this, compositions of biogas (CH₄/CO₂ = 40/60 to 80/20), S/C ratio, reformer feed temperature and heat flux have been varied. Preferable feed conditions to the reformer are total molar feed rate of 21 kmol/h, steam to methane ratio of 4.0, temperature of 973 K and pressure of 25 bar. Under these conditions, industrial reformer fed with biogas, provides methane conversion (93.08–85.65%) and hydrogen yield (1.02–2.28), that are close to thermodynamic equilibrium condition.     

Solar enriched methane production by steam reforming process: Reactor design

A novel hybrid plant for a mixture of methane and hydrogen (enriched methane) production from a steam reforming reactor whose heat duty is supplied by a molten salt stream heated up by a concentrating solar power (CSP) plant developed by ENEA is here presented. By this way, a hydrogen stream, mixed with natural gas, is produced from solar energy by a consolidated production method as the steam reforming process and by a pre-commercial technology as molten salts parabolic mirrors solar plant. After the hydrogen production plant, the residual heat stored in molten salt stream is used to produce electricity and the plant is co-generative (hydrogen + electricity).The heat-exchanger-shaped reactor is dimensioned by a design tool developed in MatLab environment. A reactor 3.5 m long and with a diameter of 2″ is the most efficient in terms of methane conversion (14.8%) and catalyst efficiency (4.7 Nm³/h of hydrogen produced per kg_cat).     

Thermodynamic analysis of fossil fuels reforming for fuel cell application

At present, the infrastructure of hydrogen production, storage and transportation is poor. Fuel reforming for hydrogen production from liquid fossil fuels such as kerosene, petrol and diesel is of great significance for wide application of on-board fuel cell and distributed energy resources. In this work, the produced and heat released of kerosene, petrol and diesel reformed by different reforming methods (autothermal reforming, partial oxidation, steam reforming) were studied by means of thermodynamic analysis. Based on the thermodynamic analysis, the effect of reforming methods on the system's ideal thermal efficiency are analysed. The results show that the hydrogen concentration of syngas obtained from steam reforming is highest regardless of the fuel types. The hydrogen yielded by per unit volume of diesel is largest under same reforming method. Autothermal reforming has the largest ideal thermal efficiency among three reforming methods.     

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.     

Modelling of the ethanol steam reforming over Rh-Pd/CeO2 catalytic wall reactors

Existing literature data have been used to model the steam reforming of ethanol on catalytic honeycombs coated with Rh-Pd/CeO₂, which have shown an excellent performance and robustness for the production of hydrogen under realistic conditions. In this article, a fully 3D non-isothermal model is presented, where the reactions of ethanol decomposition, water gas shift, and methane steam reforming have been modelled under different operational pressures (1–10 bar) and temperatures (500–1200 K) at a steam to carbon ratio of S/C = 3 and a space time of W/F between 2·10⁻³ and 3 kg h L_liq⁻¹. According to the modelling results, a maximum hydrogen yield of 80% is achieved at a working temperature of 1150 K and a pressure of 4 bar at S/C = 3.     

Experimental investigation of hydrogen production integrated methanol steam reforming with middle-temperature solar thermal energy

Developing a hydrogen production method that utilizes solar thermal energy in an effective manner is a great challenge. In this paper we propose a new approach to solar hydrogen production with the integration of methanol steam reforming and middle-temperature solar thermal energy. An experiment on hydrogen production is conducted using a 5-kW solar reactor at 150−300 °C under atmosphere pressure. The 5-kW solar receiver/reactor is fabricated and positioned along the focal line of one-tracking parabolic trough concentrator. As a result, the chemical conversion of methanol can reach levels higher than 90%, and the volumetric concentration of hydrogen in the gas products can account for 66−74% above the solar flux of 580 W/m². The obtained maximum hydrogen yield per mole of methanol is 2.65−2.90 mol, approaching the theoretical maximum value, and the experimentally obtained thermochemical efficiency of solar thermal energy converted into chemical energy is in the range of 30−50%, which is competitive with other high-temperature solar thermochemical processes. A kinetic model of solar-driven methanol steam reforming related to solar flux is also derived based on the experimental data. The promising results demonstrate that this solar-driven hydrogen production method can be feasible in practical applications.     

Upgrading waste heat from a cement plant for thermochemical hydrogen production

A calcium oxide/steam chemical heat pump (CHP) is presented in the study as a means to upgrade waste heat from industrial processes for thermochemical hydrogen production. The CHP is used to upgrade waste heat for the decomposition of copper oxychloride (CuO.CuCl₂) in a copper–chlorine (Cu–Cl) thermochemical cycle. A formulation is presented for high temperature steam electrolysis and thermochemical splitting of water using waste heat of a cement plant. Numerical models are presented for verifying the availability of energy for potential waste heat upgrading in cement plants. The optimal hydration and decomposition temperatures for the calcium oxide/steam reversible reaction of 485 K and 565 K respectively are obtained for the combined heat pump and thermochemical cycle. The coefficient of performance and overall efficiency of 4.6 and 47.8% respectively are presented and discussed for the CHP and hydrogen production from the cement plant.