Co-production of hydrogen and carbon black from solar thermal methane splitting in a tubular reactor prototype

This study addresses the solar thermal decomposition of natural gas for the co-production of hydrogen and carbon black (CB) as a high-value nano-material with the bonus of zero CO₂ emission. The work focused on the development of a medium-scale solar reactor (10 kW) based on the indirect heating concept. The solar reactor is composed of a cubic cavity receiver (20 cm-side), which absorbs concentrated solar irradiation through a quartz window by a 9 cm-diameter aperture. The reacting gas flows inside four graphite tubular reaction zones that are settled vertically inside the cavity. Experimental results in the temperature range 1740-2070 K are presented: acetylene (C₂H₂) was the most important by-product with a mole fraction of up to about 7%, depending on the gas residence time. C₂H₂ content in the off-gas affects drastically the carbon yield of the process. The effects of temperature and residence time are analyzed. A preliminary process study concerning a 55 MW solar chemical plant is proposed on the basis of a process flow sheet. Results show that 1.7 t/h of hydrogen and 5 t/h of CB could be produced with an hydrogen cost competitive to conventional steam methane reforming.     

Numerical simulation of a tubular solar reactor for methane cracking

This study addresses the solar thermal cracking of methane for the co-production of hydrogen and carbon black as a medium to avoid CO₂ emissions from natural gas combustion processes. The objective of this work is to numerically simulate the transport processes of momentum heat and mass in an indirect heating solar reactor, which is fed with an argon-methane mixture. The reactor is composed of a cubic cavity receiver, which absorbs concentrated solar irradiation through a quartz window and a graphite reaction tube is settled vertically inside this cavity. A series of numerical experiments were carried out in order to gain a better understanding of the interaction between the several transport phenomena taking place. The simulations showed that, in general, when the temperature of the reaction chamber is higher than 2000 K, the methane conversion is practically 100%. To validate our simulation results we compared them with available experimental data obtaining good agreement. Moreover, our results clearly evidence that most of the reaction takes place at the bottom of the reactor, which is the zone with the highest temperature profiles. Therefore, we propose modifications in the reactor design to increase conversion. The results of this work can thus serve to improve design and control of solar reactors for light hydrocarbons.     

Solar hydrogen production from the thermal splitting of methane in a high temperature solar chemical reactor

This study addresses the single-step thermal decomposition (pyrolysis) of methane without catalysts. The process co-produces hydrogen-rich gas and high-grade carbon black (CB) from concentrated solar energy and methane. It is an unconventional route for potentially cost effective hydrogen production from solar energy without emitting carbon dioxide since solid carbon is sequestered.A high temperature solar chemical reactor has been designed to study the thermal splitting of methane for hydrogen generation. It features a nozzle-type graphite receiver which absorbs the solar power and transfers the heat to the flow of reactant at a temperature that allows dissociation. Theoretical and experimental investigations have been performed to study the performances of the solar reactor. The experimental set-up and effect of operating conditions are described in this paper. In addition, simulation results are presented to interpret the experimental results and to improve the solar reactor concept. The temperature, geometry of the graphite nozzle, gas flow rates, and CH₄ mole fraction have a strong effect on the final chemical conversion of methane. Numerical simulations have shown that a simple tubular receiver is not enough efficient to heat the bulk gas in the central zone, thus limiting the chemical conversion. In that case, the reaction takes place only within a thin region located near the hot graphite wall. The maximum CH₄ conversion (98%) was obtained with an improved nozzle, which allows a more efficient gas heating due to its higher heat exchange area.     

Effect of reactor geometry on the temperature distribution of hydrogen producing solar reactors

Global effects of greenhouse gas emissions associated with the current extensive use of fossil fuels are increasingly attracting research groups and industry to find a solution. In order to reduce or avoid such emissions, solar thermal cracking of natural gas has been studied by many research groups as a clean and economically viable option for hydrogen production with zero CO₂ emissions. By utilization of concentrated solar energy as the source of high temperature process heat, natural gas is decomposed into hydrogen gas and high grade carbon using a solar reactor. Our previous study shows that temperature distribution inside the solar reactor has significant effect on hydrogen production. In this paper, we expand our previous study by demonstrating that reactor geometry has a notable impact on temperature distribution inside the solar reactor and therefore it has an impact on natural gas to hydrogen conversion. Results show that there are approximately 22% and 32% losses from spherical and cylindrical reactors, respectively, while hydrogen production amount varies from 1.27 g/s to 8.95 g/s for spherical reactor, and 0.94 g/s to 8.94 g/s for cylindrical reactor geometry.     

Production of enriched methane by a molten-salt concentrated solar power plant coupled with a steam reforming process: An LCA study

Enriched Methane is a gas mixture consisting of methane and a certain amount of hydrogen (10–30%vol) that finds out several applications such as fuel of Internal Combustion Engines (ICEs). To produce EM, a steam reforming reactor whose heat duty is supplied by a molten-salt stream heated up by a concentrating solar power (CSP) plant can be used, in order to generate the hydrogen steam by solar energy. In fact, molten salts at temperatures up to 550 °C can allow to reach the necessary thermal level inside the reactor to promote steam reforming reaction.     

Residence time distribution and flow field study of aero-shielded solar cyclone reactor for emission-free generation of hydrogen

This paper provides a thorough analysis on the flow field and Residence Time Distribution (RTD) of our “aero-shielded cyclone solar reactor” designed to generate hydrogen from solar thermal methane cracking process. The analysis has been carried out based on the results from flow dynamics, and residence time distribution by using Computational Fluid Dynamics (CFD). Kinetics is taken from the literature and the reactor volume is estimated based on a plug flow reactor assumption. Residence time distribution characteristics are obtained by gas tracer injection method, and particle tracking method. Based on the results of our flow studies, “reactors in series model” is adopted to model the aero-shielded cyclone reactor. Path lines show that operating variables have significant effect on the flow behavior inside the reactor. Results show that thermo chemical properties of the gases have effect on the flow behavior which significantly affect the mean residence time in the reactor. Results also show that the residence time, spread of the tracer by variance, and the number of reactors in series are observed to be changed by change in the flow rate, type of screening gas, and methane mole fraction in the feed.     

Thermal performance simulation of a solar cavity receiver under windy conditions

Solar cavity receiver plays a dominant role in the light-heat conversion. Its performance can directly affect the efficiency of the whole power generation system. A combined calculation method for evaluating the thermal performance of the solar cavity receiver is raised in this paper. This method couples the Monte-Carlo method, the correlations of the flow boiling heat transfer, and the calculation of air flow field. And this method can ultimately figure out the surface heat flux inside the cavity, the wall temperature of the boiling tubes, and the heat loss of the solar receiver with an iterative solution. With this method, the thermal performance of a solar cavity receiver, a saturated steam receiver, is simulated under different wind environments. The highest wall temperature of the boiling tubes is about 150 °C higher than the water saturation temperature. And it appears in the upper middle parts of the absorbing panels. Changing the wind angle or velocity can obviously affect the air velocity inside the receiver. The air velocity reaches the maximum value when the wind comes from the side of the receiver (flow angle α = 90°). The heat loss of the solar cavity receiver also reaches a maximum for the side-on wind.     

A pilot-scale solar reactor for the production of hydrogen and carbon black from methane splitting

A pilot-scale solar reactor was designed and operated at the 1 MW solar furnace of CNRS for H₂ and carbon black production from methane splitting. This constitutes the final objective of the SOLHYCARB EC project. The reaction of CH₄ dissociation produces H₂ and carbon nanoparticles without CO₂ emissions and with a solar upgrade of 8% of the high heating value of the products. The reactor was composed of 7 tubular reaction zones and of a graphite cavity-type solar receiver behaving as a black-body cavity. Temperature measurements around the cavity showed a homogeneous temperature distribution. The influence of temperature (1608K–1928K) and residence time (37–71 ms) on methane conversion, hydrogen yield, and carbon yield was especially stressed. For 900 g/h of CH₄ injected (50% molar, the rest being argon) at 1800K, this reactor produced 200 g/h H₂ (88% H₂ yield), 330 g/h CB (49% C yield) and 340 g/h C₂H₂ with a thermal efficiency of 15%. C₂H₂ was the most important by-product and its amount decreased by increasing the residence time. A 2D thermal model of the reactor was developed. It showed that the design of the reactor front face could be drastically improved to lower thermal losses. The optimised design could reach 77% of the ideal black-body absorption efficiency (86% at 1800K), i.e. 66%.     

Thermal and chemical reaction performance analyses of steam methane reforming in porous media solar thermochemical reactor

In order to investigate the thermochemical reaction performance of steam methane reforming (SMR), the steady heat and mass transfer model coupled with thermochemical reaction kinetics is developed for the volumetric porous media solar thermochemical reactor. The local non-thermal equilibrium (LNTE) model with modified P1 approximation is adopted to investigate the temperature distributions of the solid phase and fluid phase. For the solid phase energy equation, the irradiative heat transfer coupled with chemical reaction kinetics is programmed via User Defined Functions (UDFs). The concentrated solar irradiation is not only considered as the boundary condition at the reactor front surface, but also as the irradiative heat source in the whole volume of reactor. The parametric studies are conducted to investigate the thermal and hydrogen production performances as a function of operational parameters. The numerical results indicate that SMR reaction has big effects on temperature distribution. The generated H₂ mole fraction decreases sharply with the increasing of fluid inlet velocity, porosity and mean cell size. The generated H₂ mole fraction increases significantly with the increasing of incident solar irradiance.     

Solar thermal cracking of methane in a particle-flow reactor for the co-production of hydrogen and carbon

An experimental investigation on the thermal decomposition of CH₄ into C and H₂ was carried out using a 5 kW particle-flow solar chemical reactor tested in a solar furnace in the 1300–1600 K range. The reactor features a continuous flow of CH₄ laden with μm-sized carbon black particles, confined to a cavity receiver and directly exposed to concentrated solar irradiation of up to 1720 suns. The reactor performance was examined for varying operational parameters, namely the solar power input, seed particle volume fraction, gas volume flow rate, and CH₄ molar concentration. Methane conversion and hydrogen yield exceeding 95% were obtained at residence times of less than 2.0 s. A solar-to-chemical energy conversion efficiency of 16% was experimentally reached, and a maximum value of 31% was numerically predicted for a pure methane flow. SEM images revealed the formation filamentous agglomerations on the surface of the seed particles, reducing their active specific surface area.     

One-dimensional model of solar thermal reactors for the co-production of hydrogen and carbon black from methane decomposition

The solar thermal decomposition of methane is a promising route for the large scale production of hydrogen and carbon black with zero CO₂ emissions, however careful control of the reactor is required to ensure product particles of specific sizes. A one-dimensional model employing a sectional method is developed to simulate the evolution of polydisperse fresh and seed particle populations in an indirectly heated solar reactor. The model accounts for the homogeneous nucleation of fresh particles, the heterogeneous growth of the fresh and seed particles, particle coagulation, and the growth of carbon on the walls of the reactor from heterogeneous reaction and particle deposition. The heat transport mechanisms modelled include wall-gas convection, wall-particle radiation exchange, particle-gas convection and heat release from chemical reaction. The model is validated in terms of methane conversion against a 10 kW experimental solar reactor and used to extract kinetic parameters for the homogeneous and heterogeneous reaction paths. The model shows promise as a quick and simple tool for the design and control of industrial scale solar reactors.     

An integrated approach for the production of hydrogen and methane by catalytic hydrothermal glycerol reforming coupled with parabolic trough solar thermal collectors

An integrated catalytic hydrothermal reforming process for the production of hydrogen and methane from wet biomass feedstock is proposed where the process heat is provided by molten salts previously heated by solar energy. The simulated reactor consists of double tubes in which the reactants and the heat transfer fluid (i.e. molten salts) are concurrently pumped through the inner and the outer tubes, respectively. The first section of the reactor essentially serves as a preheater to increase the feed temperature to 20 K below the desired reaction temperature (i.e. 773 K), while the second section is comprised of a catalyst appropriate for the reforming of glycerol and water-gas shift reaction (e.g. Ru and Ni catalysts). The required energy for heating up the reactants to the final reaction temperature in the preheating section as well as the heat of reaction needed throughout the catalyst bed is provided by a co-currently fed molten salts mixture previously heated to 823 K in parabolic trough solar collectors. After heat recovery, the product mixture is cooled down to ambient temperature and depressurized to form liquid and gas phases. The gas products are subsequently separated into hydrogen, methane, and carbon dioxide or can be alternatively used for electricity generation using solid oxide fuel cells (SOFC). Glycerol was considered as a biomass model compound throughout this study, but the same methodology with minor changes can be applied to other oxygenated biomass compounds such as carbohydrates. The simulation results indicated that the degree of heat recovery has considerable effects on the process efficiency, the required parabolic mirror area, and the corresponding molten salt flow rate. Also, the higher the extent of the heat recovery, the smaller the dependence of the overall efficiency to the feed concentration.     

Experimental and simulation study on wind affecting particle flow in a solar receiver

The solid particle receiver (SPR) is a direct absorption central receiver that can provide a solar interface with thermal storage for thermo-chemical hydrogen production processes requiring heat input at temperatures up to 1000 °C. In operation, a curtain made up of approximately 697 μm ceramic particles is dropped within the receiver cavity and directly illuminated by concentrated solar energy. Since the SPR has an open aperture, the flow may be disturbed by high ambient winds. Therefore, the objective of this study was to gain insight into the wind effect on the curtain. Experiments were conducted to understand the wind influence on the particle flow and loss. The experimental results showed that winds from certain angles of the attack could cause a critical loss of particles. A MFIX simulation model was developed to validate the experimental results and observation. The simulation has provided us with better understanding on the wind effects.     

Hydrogen production by steam-gasification of petroleum coke using concentrated solar power—II Reactor design,testing, and modeling

The solar chemical reactor technology for the steam-gasification of petcoke is presented. The reactor features a continuous vortex flow of steam laden with petcoke particles confined to a cavity receiver and directly exposed to concentrated solar radiation. A 5 kW prototype reactor tested in a high-flux solar furnace in the range 1300–1800 K yielded up to 87% petcoke conversion in a single pass of 1 s residence time. The solar-to-chemical energy conversion efficiency attained 9% without accounting for the product's sensible heat, and 20% when the sensible heat is recovered for steam generation and pre-heating. A steady-state process model that couples radiative heat transfer with the reaction kinetics is validated with experimental data and used for optimization and scale-up of the reactor design.     

A thermochemical reactor design with better thermal management and improved performance for methane/carbon dioxide dry reforming

A solar thermochemical reactor with better thermal management is proposed to improve the performance for dry reforming of methane. Conical cavity is introduced in the thermochemical reactor to adjust incident solar radiation distribution. Preheating area is adopted to recover sensible heat from gas outlet. Multiphysical model is presented for analyzing the overall performance of the reactor under different inlet flow rates. Also, local ideal reaction temperature required for maximizing local hydrogen production is analyzed according to the reaction kinetics. It is shown that better synergy between real temperature distribution and ideal temperature requirement can be achieved in this new reactor. Compared with conventional reactor, the present reactor exhibits the better performance in terms of reactant conversion, energy storage efficiency and hydrogen yield. Particularly, hydrogen yield is increased by 4.31%–17.12% at inlet flow rates between 6 and 12 L min^?1.     

Hydrogen production from thermo-catalytic decomposition of methane using carbon black catalysts in an indirectly-irradiated tubular packed-bed solar reactor

The solar thermo-catalytic decomposition of methane using carbon black catalysts for CO₂-free hydrogen production is studied in a packed-bed reactor. The indirectly-irradiated reactor is based on a cavity receiver and a tube-type absorber in which a given load of particle catalyst is injected during on-sun operation, while enabling multiple refilling for catalyst replacement. Concentrated solar power is used as an external radiative source for supplying the high temperature process heat and for driving the endothermic reaction. The indirect irradiation via the intermediate opaque tubular absorber results in a more uniform heating of the whole reacting bed volume and thus an easier reaction temperature control and determination. Carbon particles are used for enhancing the rate of the heterogeneous decomposition reaction and the coupling of the reactor with a particle injection system is implemented to operate in semi-continuous mode with possibility of catalyst load renewal after deactivation.     

Further advances toward the development of a direct heating solar thermal chemical reactor for the thermal dissociation of ZnO(s)

We designed, built and experimentally tested a solar thermal chemical reactor for producing Zn from ZnO(s). We describe the salient features of the reactor concept, the design process itself, and initial experimental results from testing the reactor under solar conditions for both the thermal reduction of ZnO(s) and the carbothermal reduction of the oxide. The reactor operated reliably for more than 100 h. Reactor cavity temperatures reached 2000 K. For the carbothermal reduction of ZnO(s), the solid product was Zn with a purity exceeding 95 mol%. For this reaction, we report reactor and process efficiencies versus cavity temperature. Average values were as high as 14% and 12% respectively. There is an optimal operating temperature and feed condition for these efficiencies: the positive effect of high reaction rates at high temperatures must be balanced against high radiation losses from the reactor at high temperatures. At the operating conditions leading to the highest efficiencies, we produced 1.5 moles of Zn for each mole of consumed carbon. Although the reactor operated mechanically as expected for the thermal reduction of ZnO(s), we were not yet able to obtain high Zn yields.     

Solar water splitting for hydrogen production with monolithic reactors

The present work proposes the exploitation of solar energy for the dissociation of water and production of hydrogen via an integrated thermo-chemical reactor/receiver system. The basic idea is the use of multi-channelled honeycomb ceramic supports coated with active redox reagent powders, in a configuration similar to that encountered in automobile exhaust catalytic aftertreatment.Iron-oxide-based redox materials were synthesized, capable to operate under a complete redox cycle: they could take oxygen from water producing pure hydrogen at reasonably low temperatures (800 °C) and could be regenerated at temperatures below 1300 °C. Ceramic honeycombs capable of achieving temperatures in that range when heated by concentrated solar radiation were manufactured and incorporated in a dedicated solar receiver/reactor. The operating conditions of the solar reactor were optimised to achieve adjustable, uniform temperatures up to 1300 °C throughout the honeycomb, making thus feasible the operation of the complete cycle by a single solar energy converter.     

Kinetic investigation of hydrogen generation from hydrolysis of SnO and Zn solar nanopowders

The hydrolysis reaction of the two-step ZnO/Zn and SnO₂/SnO thermochemical cycles was kinetically investigated for solar hydrogen production. Nanoparticles of Zn and SnO were synthesized by solar thermal reduction of the oxides and neutral gas quenching of the vapors. They were then hydrolyzed to quantify and compare the H₂ yields and the kinetic rate laws in fixed-bed. The hydrolysis of Zn nanoparticles reached only up to 55% of H₂ yield, whereas SnO hydrolysis was almost complete. In contrast, Zn hydrolysis was much faster than SnO hydrolysis, but Zn deactivation occurred suddenly. Models of solid–gas reactions were applied to identify the controlling mechanisms and the associated kinetic parameters. The kinetic models were fitted to both isothermal and non-isothermal (temperature ramp) hydrolysis experimental data. Activation energies and reaction orders were found to be 122 ± 13 kJ/mol and 2.0 ± 0.3 for SnO, and 87 ± 7 kJ/mol and 3.5 ± 0.5 for Zn, respectively. Finally, a shrinking core approach was applied to the case of SnO to account for the reaction-controlling mechanisms.     

Enriched methane production using solar energy: an assessment of plant performance

A novel hybrid plant for the production of a mixture of methane and hydrogen (17 vol%) from a steam-reforming reactor whose heat duty is supplied by a concentrating solar power (CSP) plant by means of a molten salt stream is here presented.