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.     

Thermodynamic assessment of modified Organic Rankine Cycle integrated with parabolic trough collector for hydrogen production

Hydrogen is one of the most clean energy carrier and the best alternative for fossil fuels. In this study, thermodynamic analysis of modified Organic Rankine Cycle (ORC) integrated with Parabolic Trough Collector (PTC) for hydrogen production is investigated. The integrated system investigated in this study consists of a parabolic trough collector, a modified ORC, a single effect absorption cooling system and a PEM electrolyzer. By using parabolic trough collector, solar energy is converted heat energy and then produced heat energy is used in modified ORC to produce electricity. Electricity is then used for hydrogen production. The outputs of this integrated system are electricity, cooling and hydrogen. By performing a parametric study, the effects of design parameters of PTC, modified ORC and PEM electrolyzer on hydrogen production is evaluated. According to the analysis results, solar radiation is one of the most important factor affecting system exergy efficiency and hydrogen production rate. As solar radiation increases from 400?W/m² to 1000?W/m², exergy efficiency of the system increases 58%–64% and hydrogen production rate increases from 0.1016?kg/h to 0.1028?kg/h.     

Effect of using nanofluids on efficiency of parabolic trough collectors in solar thermal electric power plants

In this paper, forced convection heat transfer nanofluid flow inside the receiver tube of solar parabolic trough collector is numerically simulated. Computational Fluid Dynamics (CFD) simulations are carried out to study the influence of using nanofluid as heat transfer fluid on thermal efficiency of the solar system. The three-dimensional steady, turbulent flow and heat transfer governing equations are solved using Finite Volume Method (FVM) with the SIMPLEC algorithm. The results show that the numerical simulation are in good agreement with the experimental data. Also, the effect of various nanoparticle volume fraction on thermal and hydrodynamic characteristics of the solar parabolic collector is discussed in details. The results indicate that, using of nanofluid instead of base fluid as a working fluid leads to enhanced heat transfer performance. Furthermore, the results reveal that by increasing of the nanoparticle volume fraction, the average Nusselt number increases.     

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.     

Performance model for parabolic trough solar thermal power plants with thermal storage: Comparison to operating plant data

This paper describes a simulation model that reproduces the performance of parabolic trough solar thermal power plants with a thermal storage system. The aim of this model is to facilitate the prediction of the electricity output of these plants during the various stages of their planning, design, construction and operation. Model results for a 50 MW_e power plant are presented and compared to real data from an equivalent power plant currently operated by the ACS Industrial Group in Spain.     

Influence of hydrothermal treatment on structural property of NiZrAl mixed-metal oxides and on catalytic steam reforming of glycerol for hydrogen production

NiZrAl layered double hydroxides (LDH) precursors were synthesized by co-precipitation and homogeneous precipitation processes. The introduction of hydrothermal treatment into crystallization showed its significant influences on structure of LDH as well as mixed-metal oxides after thermal decomposition. The characterization results showed that the catalysts prepared by hydrothermal synthesis involved bigger pore diameter of ca. 13.5 nm and wider pore size distribution of 2–60 nm, and hydrothermal treatment was helpful to enhance the reduction of NiO species weakly interacted with support and to enhance the interaction among the metal oxides. Although the Ni dispersion, the surface area as well as the ability of anti-sintering were evidently improved, the ability of coke resistance decreased by 2 times for samples prepared by co-precipitation and by nearly 10 times for the ones prepared by homogeneous precipitation due to the enlarged pores. The maximum value of conversion to gaseous products (96.5%) and minimum deposited coke (36 m_gc/g_cat.) were achieved on NiZrAl-u sample.     

Design, manufacture and testing of fiberglass reinforced parabola trough for parabolic trough solar collectors

The design and manufacture of a smooth 90° rim angle fiberglass reinforced parabolic trough for parabolic trough solar collector hot water generation system by hand lay up method is described in this paper. The total thickness of the parabolic trough is 7 mm. The concave surface where the reflector is fixed is manufactured to a high degree of surface finish. The fiberglass reinforced parabolic trough was tested under a load corresponding to the force applied by a blowing wind with 34 m/s. Distortion of the parabola due to wind loading was found to be within acceptable limits. The thermal performance of the newly developed fiberglass reinforced parabolic collector was determined according to ASHRAE Standard 93 [ASHRAE Standard 93, 1986. Method of testing to determine the thermal performance of solar collectors. American Society of Heating, Refrigerating and Air-Conditioning Engineers, Atlanta, GA]. The standard deviation of the distribution of the parabolic surface errors is estimated as 0.0066 rad from the collector performance test according to ASHRAE Standard 93 (1986), which indicates the high accuracy of the parabolic surface.     

Solar multiple optimization for a solar-only thermal power plant, using oil as heat transfer fluid in the parabolic trough collectors

Usual size of parabolic trough solar thermal plants being built at present is approximately 50 MW_e. Most of these plants do not have a thermal storage system for maintaining the power block performance at nominal conditions during long non-insolation periods. Because of that, a proper solar field size, with respect to the electric nominal power, is a fundamental choice. A too large field will be partially useless under high solar irradiance values whereas a small field will mainly make the power block to work at part-load conditions.This paper presents an economic optimization of the solar multiple for a solar-only parabolic trough plant, using neither hybridization nor thermal storage. Five parabolic trough plants have been considered, with the same parameters in the power block but different solar field sizes. Thermal performance for each solar power plant has been featured, both at nominal and part-load conditions. This characterization has been applied to perform a simulation in order to calculate the annual electricity produced by each of these plants. Once annual electric energy generation is known, levelized cost of energy (LCOE) for each plant is calculated, yielding a minimum LCOE value for a certain solar multiple value within the range considered.     

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.     

The integration of parabolic trough solar collectors and evacuated tube collectors to geothermal resource for electricity and hydrogen production

In this study, electricity and hydrogen production of an integrated system with energy and exergy analyses are investigated. The system also produces clean water for the water electrolysis system. The proposed system comprises evacuated tube solar collectors (ETSCs), parabolic trough solar collectors (PTSCs), flash turbine, organic Rankine cycles (ORC), a reverse osmosis unit (RO), a water electrolysis unit (PEM), a greenhouse and a medium temperature level geothermal resource. The surface area of each collector is 500 m². The thermodynamics analysis of the integrated system is carried out under daily solar radiation for a day in August. The fluid temperature of the medium temperature level geothermal resource is upgraded by ETSCs and PTSCs to operate the flash turbine and the ORCs. The temperature of the geothermal fluid is upgraded from 130 °C to 323.6 °C by the ETSCs and PTSCs. As a result, it is found that the integrated system generates 162 kg clean water, 1215.63 g hydrogen, and total electrical energy of 2111.04 MJ. The maximum energy and exergy efficiencies of the overall system are found as 10.43% and 9.35%, respectively.     

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 by glycerol steam reforming with in situ hydrogen separation: A thermodynamic investigation

Thermodynamic features of hydrogen production by glycerol steam reforming with in situ hydrogen extraction have been studied with the method of Gibbs free energy minimization. The effects of pressure (1–5 atm), temperature (600–1000 K), water to glycerol ratio (WGR, 3–12) and fraction of H₂ removal (f, 0–1) on the reforming reactions and carbon formation were investigated. The results suggest separation of hydrogen in situ can substantially enhance hydrogen production from glycerol steam reforming, as 7 mol (stoichiometric value) of hydrogen can be obtained even at 600 K due to the hydrogen extraction. It is demonstrated that atmospheric pressure and a WGR of 9 are suitable for hydrogen production and the optimum temperature for glycerol steam reforming with in situ hydrogen removal is between 825 and 875 K, 100 K lower than that achieved typically without hydrogen separation. Furthermore, the detrimental influence of increasing pressure in terms of hydrogen production becomes marginal above 800 K with a high fraction of H₂ removal (i.e., f = 0.99). High temperature and WGR are favorable to inhibit carbon production.     

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.     

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.     

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 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.     

Performance analysis of an Integrated Solar Combined Cycle using Direct Steam Generation in parabolic trough collectors

The contribution of solar thermal power to improve the performance of gas-fired combined cycles in very hot and dry environmental conditions is analyzed in this work, in order to assess the potential of this technique, and to feature Direct Steam Generation (DSG) as a well suited candidate for achieving very good results in this quest. The particular Integrated Solar Combined Cycle (ISCC) power plant proposed consists of a DSG parabolic trough field coupled to the bottoming steam cycle of a Combined Cycle Gas Turbine (CCGT) power plant. For this analysis, the solar thermal power plant performs in a solar dispatching mode: the gas turbine always operates at full load, only depending on ambient conditions, whereas the steam turbine is somewhat boosted to accommodate the thermal hybridization from the solar field.     

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.     

A detailed nonuniform thermal model of a parabolic trough solar receiver with two halves and two inactive ends

In this paper a detailed one dimensional nonuniform thermal model of a parabolic trough solar collector/receiver is presented. The entire receiver is divided into two linear halves and two inactive ends for the nonuniform solar radiation, heat transfers and fluid dynamics. Different solar radiation and heat transfer modes can be taken into consideration for these four different regions respectively. This enables the study of different design parameters, material properties, operating conditions, fluid flow and heat transfer performance for the corresponding regions or the whole receiver. Then the nonuniform model and the corresponding uniform thermal model are validated with known performance of an existing parabolic trough solar collector/receiver. For applications, the uniform thermal model can be used to quickly compute the integral heat transfer performance of the whole PTC system while the nonuniform thermal model can be used to analyze the local nonuniform solar radiation and heat transfer performance characteristics and nonuniform heat transfer enhancements or optimizations. Later, it could also be effectively used with an intelligent optimization, such as the genetic algorithm or the particle swarm optimization, to quickly evaluate and optimize the characteristics and performance of PTCs under series of nonuniform conditions in detail.     

Modelling of parabolic trough direct steam generation solar collectors

Solar electric generation systems (SEGS) currently in operation are based on parabolic trough solar collectors using synthetic oil heat transfer fluid in the collector loop to transfer thermal energy to a Rankine cycle turbine via a heat exchanger. To improve performance and reduce costs direct steam generation in the collector has been proposed. In this paper the efficiency of parabolic trough collectors is determined for operation with synthetic oil (current SEGS plants) and water (future proposal) as the working fluids. The thermal performance of a trough collector using Syltherm 800 oil as the working fluid has been measured at Sandia National Laboratory and is used in this study to develop a model of the thermal losses from the collector. The model is based on absorber wall temperature rather than fluid bulk temperature so it can be used to predict the performance of the collector with any working fluid. The effects of absorber emissivity and internal working fluid convection effects are evaluated. An efficiency equation for trough collectors is developed and used in a simulation model to evaluate the performance of direct steam generation collectors for different radiation conditions and different absorber tube sizes. Phase change in the direct steam generation collector is accounted for by separate analysis of the liquid, boiling and dry steam zones.