Effect of seeding on hydrogen and carbon particle production in a 10 MW solar thermal reactor for methane decomposition

Solar methane decomposition reactors are a novel technology for the production of carbon neutral hydrogen; however, the impact of this technology depends greatly on the ability to co-produce carbon black particles of commercial grade in order to offset the cost of hydrogen production and, therefore, the control of the reactor is very important. To this end, the seeding of indirect heating concept reactors using the product particles themselves could be used to control heat transfer inside the reactor. In this work, a previously developed one-dimensional reactor – particle population model was used to simulate the effect of seeding on the hydrogen and carbon particle production rates in the absorber tubes of a 10 MW indirect heating concept solar reactor. It was found that seed particle feed rates less than 10% of the methane-contained carbon feed rate allowed the hydrogen and fresh particle production rates to be doubled while keeping the rate of carbon growth on the tube walls constant. It was also found that similar seed fee rates could be used to maintain the hydrogen and particle production rates constant, given variations in the absorber tube wall temperature within a 100 °C range, for example due to cloud passage. Furthermore, it was found that the size characteristics of the freshly produced particles were not affected at these seed feed rates. Thus, seeding could be an effective means for increasing and controlling the hydrogen and carbon particle production rates in industrial scale indirect heating concept solar methane decomposition reactors, while also reducing carbon growth on the walls of the absorber tubes.     

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.     

Particle–gas reacting flow under concentrated solar irradiation

A transient heat transfer model is developed for a reacting flow of CH₄ laden with carbon particles directly exposed to concentrated solar radiation and undergoing thermal decomposition into carbon and hydrogen. The unsteady mass and energy conservation equations, coupling convective heat and mass transfer, radiative heat transfer, and chemical kinetics for a two-phase solid–gas flow, are formulated and solved numerically for both phases by Monte Carlo and finite volume methods using the explicit Euler time integration scheme. Parametric study is performed with respect to the initial particle diameter, volume fraction, gas composition, and velocity. Validation is accomplished by comparing temperatures and reaction extent with those measured experimentally using a particle-flow solar reactor prototype subjected to concentrated solar radiation. Smaller particles and/or high volume fractions increase the optical thickness of the medium, its radiative absorption and extinction coefficients, and lead to higher steady-state temperatures, reaction rates, and consequently, higher extent of chemical conversion.     

Sensitivity analysis of the rapid decomposition of methane in an aerosol flow reactor

A one-dimensional, nonisothermal model is developed to describe the thermal dissociation of methane to hydrogen and carbon black occurring in a fluid-wall aerosol flow reactor. The model expressions are scaled and nondimensionalized to determine the minimum parametric representation of the system. The sensitivity of this thermal dissociation to three parameters (flow rate of carbon particles fed to initiate the reaction, carbon particle radius, and reactor wall temperature) is studied. The results of the study indicate that in order to achieve nearly complete conversion, high reactor wall temperatures must be maintained. In addition, micron-sized carbon black particles must be fed into the reactor to enhance the heat transfer to the gas phase. The actual flow rate of particles fed is not critical, as long as some flow rate of fine particles is maintained.     

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.     

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.     

Step-by-step methodology of developing a solar reactor for emission-free generation of hydrogen

This study presents a methodology to develop a solar reactor based on the thermodynamics and kinetics of methane decomposition to produce hydrogen with no emissions. The kinetic parameters were obtained in the literature for two cases; methane laden with carbon particles and methane without carbon particles. Results show that there is significant difference in experimentally obtained and theoretically predicted methane conversion. The paper also presents a parametric study on the effects of temperature, pressure and the influence of inert gas composition, which is fed along with methane, on the thermodynamics of methane decomposition. Results show that there is significant effect of the inert gas presence in the feeding gas mixture on the equilibrium of methane conversion and product gas composition. Results also show that higher conversions are obtained when the carbon particles laden with methane. The step-by-step reactor design methodology for homogenous methane decomposition and the parametric study results presented in this paper can provide a very useful tool in guiding a solar reactor design and optimization of process operating conditions.     

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.     

Heat transfer model and scale-up of an entrained-flow solar reactor for the thermal decomposition of methane

The solar thermochemical decomposition of CH₄ is carried out in a solar reactor consisting of a cavity-receiver containing an array of tubular absorbers, through which CH₄ flows and thermally decomposes to H₂ and carbon particles. A reactor model is formulated by coupling radiation/convection/conduction heat transfer and chemical kinetics for a two-phase solid-gas reacting flow. Experimental validation is accomplished by comparing measured and simulated absorber temperatures and H₂ concentrations for a 10 kW prototype reactor tested in a solar furnace. The model is applied to optimize the design and simulate the performance of a 10 MW commercial-scale reactor mounted on a solar tower system configuration. Complete conversion is predicted for a maximum CH₄ mass flow rate of 0.70 kg s⁻¹ and a desired outlet temperature of 1870 K, yielding a solar-to-chemical energy conversion efficiency of 42% and a solar-to-thermal energy conversion efficiency of 75%.     

Influence of process parameters on direct solar-thermal hydrogen and graphite production via methane pyrolysis

Current hydrogen and carbon production technologies emit massive amounts of CO₂ that threaten Earth's climate stability. Here, a new solar-thermal methane pyrolysis process involving flow through a fibrous carbon medium to produce hydrogen gas and high-value graphitic carbon product is presented and experimentally quantified. A 10 kW_e solar simulator is used to instigate the methane decomposition reaction with direct irradiation in a custom solar reactor. From localized solar heating of fibrous medium, the process reaches steady-state thermal and chemical operation from room temperature within the first minute of irradiation. Additionally, no measurable carbon deposition occurs outside the fibrous medium, leaving the graphitic product in a form readily extractable from the solar reactor. Parametric variations of methane inlet flow rate (10–2000 sccm), solar power (0.92–2.49 kW) and peak flux (1.3–3.5 MW/m²), operating pressure (1.33–40 kPa), and medium thickness (0.36–9.6 mm) are presented, with methane conversion varying from 22% to 96%.     

CFD analysis on the influence of helical carving in a vortex flow solar reactor

Solar thermal cracking of natural gas is a promising technology, which has attracted researchers in recent years for its potential to lead to the development of CO₂ free hydrogen production process. However, experimental access to the reaction chamber of solar cracking reactors is a challenge due to the high temperature process as the instruments capable of measuring fluid flow cannot survive the medium inside the reactor. However, computational fluid dynamics (CFD) can provide an insight into the flow, where experimental access is limited or not possible. This paper presents a CFD analysis for directly irradiated solar thermochemical reactor to characterize the influence of flow behavior on the heat transfer and solar cracking process. The heat transfer by radiation from carbon particles is considered by providing global absorption and scattering coefficients in the computational domain obtained from Mie code. The flow field is based on RNG k–? model derived using renormalization group theory. This technique accounts for the effect of swirl on turbulence thereby enhancing accuracy for the swirl flows. Validation of the numerical results is carried out by making a comparison with the experimental results. Highlighting the effects of carving on the solar reactor walls, this study presents numerical analyses of solar reactor geometry for two cases; namely, when there is no vortex forming carving in the cavity, and when there is vortex forming helical carving. The results show that carving has significant influence on the flow behavior, however, it has very little effect on the outlet temperature. The numerical results also show that the radiative heat transfer mechanism is the dominant means of heat transfer compared to the effects of conduction and convection.     

High-pressure catalytic combustion of methane over platinum: In situ experiments and detailed numerical predictions

The catalytic combustion of fuel-lean methane/air premixtures over platinum was investigated experimentally and numerically in the pressure range 4 to 16 bar. Experiments were performed in an optically accessible, laminar channel-flow catalytic reactor. In situ, spatially resolved Raman measurements of major species and temperature over the reactor boundary layer were used to assess the heterogeneous (catalytic) reactivity and planar laser-induced fluorescence (LIF) of the OH radical confirmed the absence of homogeneous (gas-phase) ignition. Numerical predictions were carried out with a two-dimensional elliptic code that included elementary heterogeneous and homogeneous chemical reaction schemes. Comparisons between measurements and numerical predictions have led to the assessment of the high-pressure validity of two different elementary heterogeneous chemical reaction schemes for the complete oxidation of methane over platinum. It was shown that the catalytic reactivity increased with increasing pressure and that crucial in the performance of the heterogeneous reaction schemes was the capture of the decrease in surface free-site availability with increasing pressure. Even in the absence of homogeneous ignition, the contribution of the gaseous reaction pathway to the conversion of methane could not be ignored at high pressures. The delineation of the regimes of significance for both heterogeneous and homogeneous pathways has exemplified the importance of the preignition gaseous chemistry in many practical high-pressure catalytic combustion systems. Sensitivity and reaction flux analyses were carried out on a validated elementary heterogeneous reaction scheme and led to the construction of reduced catalytic reaction schemes capable of reproducing accurately the catalytic methane conversion in the channel-flow configuration as well as in a surface perfectly stirred reactor (SPSR) and, when coupled to a homogeneous reaction scheme, the combined heterogeneous and homogeneous methane conversions. A global catalytic step could not reproduce the measured catalytic reactivity over the entire pressure range 4 to 16 bar.     

Hydrogen production by steam-gasification of carbonaceous materials using concentrated solar energy – V. Reactor modeling,optimization, and scale-up

A chemical reactor for the steam-gasification of carbonaceous particles (e.g. coal, coke) is considered for using concentrated solar radiation as the energy source of high-temperature process heat. A two-phase reactor model that couples radiative, convective, and conductive heat transfer to the chemical kinetics is applied to optimize the reactor geometrical configuration and operational parameters (feedstock's initial particle size, feeding rates, and solar power input) for maximum reaction extent and solar-to-chemical energy conversion efficiency of a 5 kW prototype reactor and its scale-up to 300 kW. For the 300 kW reactor, complete reaction extent is predicted for an initial feedstock particle size up to 35 μm at residence times of less than 10 s and peak temperatures of 1818 K, yielding high-quality syngas with a calorific content that has been solar-upgraded by 19% over that of the petcoke gasified.     

Evaluation of activated carbons based on olive stones as catalysts during hydrogen production by thermocatalytic decomposition of methane

Catalytic decomposition of methane over carbon materials has been intensively studied as an environmental approach for CO₂-free hydrogen production without further by-products except hydrogen and valuable carbon. In this work, we will investigate the catalytic activity of activated carbons based on olive stones prepared by two different processes. Additionally, the effect of three major operational parameters: temperature, weight of catalyst and flow rate of methane, was determined. Therefore, a series of experiments were conducted in a horizontal-flow fixed bed reactor. The outflow gases were analysed using a mass spectrometer. The textural, structural and surface chemistry properties of both fresh and used activated carbons were determined respectively by N₂ gas adsorption, X-Ray Diffraction and Raman and Temperature Programmed Desorption. The results reveal that methane decomposition rate increases with temperature and methane flow however it decreases with catalyst weight. The two carbon samples exhibit a high initial activity followed by a rapid decay. Textural characterization of the deactivated carbon presents a dramatic drop of surface area, pore and micropore volumes against an increase of average pore diameter confirming that methane decomposition occurs mainly in micropores. XRD characterization shows a turbostratic structure of fresh samples with more graphitization in deposed carbon explaining the lowest activity at the end of reaction. Raman spectra reveal the domination of the two bands G and D which varying intensities affirm that the different carbons tend to organise in aromatic rings. Finally the surface chemistry qualitatively changes greatly after methane dissociation for CAGOC unlike CAGOP but quantitatively a small difference is observed which indicates that these functionalities may have a role in this heterogeneous reaction but cannot be totally responsible. Among the two catalysts tested, CAGOC has the highest initial methane decomposition rate but CAGOP is the most stable one.     

太阳能热化学反应器多场耦合及协同优化研究

以太阳能高温热化学反应器作为研究对象,针对甲烷还原氧化铈分解水制氢的两步法热化学循环过程,建立耦合光学、流动与传热、化学反应动力学及组分输运的多物理场模型,与实验结果对比验证模型精确性;研究各场之间的耦合机制及其对提升太阳能燃料转化效率的影响机理,提出太阳能反应器内的光-热-化学过程之间的协同优化方法。结果表明：甲烷氧化放热与氧化铈还原吸热互相作用使得催化剂温度存在波动;提高催化剂质量,同时辅以适当的光功率与反应物流量,反应物产率可得到进一步提升,太阳能-化学能转化效率最大可达到38.75%。     

A heterogeneous dynamic model for the simulation and optimisation of the steam methane reforming reactor

In the current paper the dynamic behaviour of an industrial heterogeneous catalytic packed-bed reactor for the steam reforming of methane is examined. The model consists of a set of partial differential equations describing the physico-chemical processes that take place both in solid and gas phases accounting for diffusional limitations within the catalyst particles. The model was validated against literature data, while the heat provided to the reactor wall was optimised in terms of the optimal H₂ yield using a quadratic wall temperature profile. The values of the physico-chemical properties were adjusted to the severe operating conditions (high pressures and temperatures) of the reactor accounting for multicomponent gas mixture properties. It is shown that the 2-phase reactor concept along with the optimised wall temperature profile capture very well the dynamic conversion, the temperature and the partial pressure profiles both at bed and at particle level.     

Study of cracking of methane for hydrogen production using concentrated solar energy

In this study, the cracking phenomenon of methane taking place in a cylindrical cavity of 16 cm in diameter and 40 cm in length under the heat of concentrated solar radiation without any catalyst is analysed. Three cases have been chosen; in all cases the primary phase contains methane and hydrogen gases. In the first case, we consider two phases; the secondary phase is a homogeneous carbon black powder with 50 nm of diameter; in the second case we have three phases where the two secondary phases are a particles powder with two diameters 20 and 80 nm and finally, a third case of five phases with a powder of four different diameters 20, 40, 60 and 80 nm. The low Reynolds K-ε turbulence model was applied. A calculation code "ANSYS FLUENT" is used to simulate the cracking phenomena where an Eulerian – Eulerian model is applied. The choice of several diameters greatly increases the calculation time but it approaches more of the physical reality of the radiation by these particles during the cracking. Results have shown that increasing the number of diameters gives higher cracking rates; the case of the powder of 4 different diameters gives the highest cracking rate. A parametric study as a function of the inlet velocity, carbon particle diameters and the intensity of solar radiation is realized. For the cracking heat, provided by the choice of the two concentrators of 5 and 16 MW/m² used in this simulation, the CH₄ inlet velocity is a decisive parameter for the cracking rate. Any increase in the inlet velocity requires more heat and this leads to a decrease in the cracking rate. For a velocity not exceeding 0.177 m/s (i.e. 0.3 L/min), both solar concentrations give the same amount of hydrogen produced. These quantities of hydrogen obtained reach maximum values for an inlet flow rate of CH₄ between 0.58 L/min (i.e. 0.34 m/s) and 0.62 L/min (i.e. 0.3655 m/s) for both reactors. The results are interpreted and compared with experimental work.     

Heat transfer analysis of thermal disassociation of ZnO for solar hydrogen production

Hydrogen production by the two-step solar thermochemical cycle has high cycle efficiency, low cost, and a great development space. Of special interest is the solar thermochemical cycle based on ZnO/Zn redox reactions since its high theoretical hydrogen yield and relatively low endothermic reaction temperature. In this paper, a steady heat transfer model for thermal ZnO dissociation in a solar thermochemical reactor is developed, coupling conduction, convection and radiation with chemical reaction. Accuracy was evaluated by comparison of results obtained from other references. Based on the new proposed reactor, the model is adopted to analyze the operating parameter effect on the conversion rate and fluid feature inside the solar reactor. The results show that the mass flow rate of ZnO and aperture gas temperature have a positive relation with ZnO conversion rate, however, the diameter of particles and aperture gas velocity has an inverse relation with ZnO conversion rate under specific condition. The results will provide useful foundation for improving the solar-to-fuel conversion rate in the near future.     

Decomposition of limestone in a solar reactor

The thermal decomposition of limestone has been selected as a model reaction for developing and testing an atmospheric open solar reactor. The reactor consists of a cyclone gas/particle separator which has been modified to let the concentrated solar energy enter through a windowless aperture. The reacting particles are directly exposed to the solar irradiation. Experimentation with a 60 kW reactor prototype was conducted at PSI's 90m² parabolic solar concentrator, in a continuous mode of operation. A counter-current flow heat exchanger was employed to preheat the reactants. Eighty five percent degree of calcination was obtained for cement raw material and 15% of the solar input was converted into chemical energy (enthalpy).The technical feasibility of the solar thermal decomposition of limestone was experimentally demonstrated. The use of solar energy as a source for high-temperature process heat offers the potential of reducing significantly the CO₂ emissions from lime producing plants. Such a solar thermochemical process can find application in sunny rural areas for avoiding deforestation.     

Lagrangian characterization of multi-phase turbulent flow in a solar reactor for particle deposition prediction

Solar cracking of methane is a promising technology for emission free hydrogen production. One of the major problems affecting methane cracking solar reactors' performance is the carbon particle deposition on the window, walls, and at the exit. In present study, a Lagrangian particle dispersion model has been implemented for predicting the particle deposition on the window of a seeded solar thermal reactor. A three-dimensional Computational Fluid Dynamics (CFD) analysis using Discrete Phase Model (DPM) has been done for qualitative validation of the experimental observations. In order to evaluate the turbulent quantities in the solar reactor; RNG k–? model has been applied. Species transport has been solved by taking the gas for window screening as different from that used in the main flow. In addition, this paper presents a thorough parametric study predicting the particle deposition on reactor window for various flow configurations and flow conditions, which can be summarized as; (1) when the inlet flow angle is smaller, higher tangential velocities or swirl strength is obtained, (2) higher tangential velocities help in maintaining a stronger swirl, which keeps the screening flow close to the reactor window, (3) by increasing the main flow and the screening flow rates, the particle deposition on window is reduced, (4) when a lower density fluid is used as window screening gas, the particle deposition is reduced because the Taylor instabilities are avoided. The CFD work and the findings presented in this paper would be used as a guide in designing a solar reactor or improving the configuration of existing reactor.