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%.     

Hydrogen production via sulfur-based thermochemical cycles: Part 2: Performance evaluation of Fe2O3-based catalysts for the sulfuric acid decomposition step

The sulfuric acid dissociation reaction, via which the production of SO₂ and O₂ is achieved, is the most energy intensive step of the so-called sulfur-based thermochemical cycles for the production of hydrogen. Efforts are focused on the feasibility and effectiveness of performing this reaction with the aid of a high-temperature energy/heat source like the sun. Such coupling can be achieved either directly in a solar reactor by concentrated solar radiation, or indirectly by means of a heat-exchanger/decomposer reactor using a suitable heat transfer fluid. Since a very limited amount of work regarding the potential formulations and sizing of such suitable reactors has been performed so far, the present work addresses further steps necessary for the efficient design, manufacture and operation of such reactors for sulfuric acid decomposition. In this respect, parametric studies on the SO₃ decomposition with iron(III) oxide-based catalysts were performed investigating the effect of temperature, pressure and space velocity on SO₃ conversion. Based on these results, an empirical kinetic law suitable for the reactor design was developed. In parallel, siliconised silicon carbide honeycombs coated with iron(III) oxide were prepared and tested in structured laboratory-scale reactors to evaluate their durability (i.e. activity vs. time) during SO₃ decomposition, with the result of satisfactory and stable performance for up to 100 h of operation. The results in combination with characterization results of “aged” materials can provide valuable input for the design of prototype reactors for sulfuric acid decomposition.     

CO2 and H2O reduction by solar thermochemical looping using SnO2/SnO redox reactions: Thermogravimetric analysis

The thermochemical dissociation of CO₂ and H₂O from reactive SnO nanopowders is studied via thermogravimetry analysis. SnO is first produced by solar thermal dissociation of SnO₂ using concentrated solar radiation as the high-temperature energy source. The process targets the production of CO and H₂ in separate reactions using SnO as the oxygen carrier and the syngas can be further processed to various synthetic liquid fuels. The global process thus converts and upgrades H₂O and captured CO₂ feedstock into solar chemical fuels from high-temperature solar heat only, since the intermediate oxide is not consumed but recycled in the overall process. The objective of the study was the kinetic characterization of the H₂O and CO₂ reduction reactions using reactive SnO nanopowders synthesized in a high-temperature solar chemical reactor. SnO conversion up to 88% was measured during H₂O reduction at 973 K and an activation energy of 51 ± 7 kJ/mol was identified in the temperature range of 798-923 K. Regarding CO₂ reduction, a higher temperature was required to reach similar SnO conversion (88% at 1073 K) and the activation energy was found to be 88 ± 7 kJ/mol in the range of 973-1173 K with a CO₂ reaction order of 0.96. The SnO conversion and the reaction rate were improved when increasing the temperature or the reacting gas mole fraction. Using active SnO nanopowders thus allowed for efficient and rapid fuel production kinetics from H₂O and CO₂.     

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%.     

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.     

Design,simulation and experimental study of a directly-irradiated solar chemical reactor for hydrogen and syngas production from continuous solar-driven wood biomass gasification

The use of concentrated solar energy as the high-temperature heat source for the thermochemical gasification of biomass is a promising prospect for producing CO₂-neutral chemical fuels (syngas). The solar process saves biomass resource because partial combustion of the feedstock is avoided, it increases the energy conversion efficiency because the calorific value of the feedstock is upgraded by the solar power input, and it also reduces the need for downstream gas cleaning and separation because the gas products are not contaminated by combustion by-products. A new concept of solar spouted bed reactor with continuous biomass injection was designed in order to enhance heat transfer in the reactor, to improve the gasification rates and gas yields by providing constant stirring of the particles, and to enable continuous operation. Thermal simulations of the prototype were performed to calculate temperature distributions and validate the reactor design at 1.5 kW scale. The reliable operation of the solar reactor based on this new design was also experimentally demonstrated under real solar irradiation using a parabolic dish concentrator. Wood particles were continuously gasified at temperatures ranging from 1100 °C to 1300 °C using either CO₂ or steam as oxidizing agent. Carbon conversion rates over 94% and gas productions over 70 mmol/g_biomass were achieved. The energy contained in the biomass was upgraded thanks to the solar energy input by a factor of up to 1.21.     

Hybrid sulfur flowsheets using PEM electrolysis and a bayonet decomposition reactor

A conceptual design is presented for a hybrid sulfur process for the production of hydrogen using a high-temperature nuclear heat source to split water. The process combines proton exchange membrane-based SO₂-depolarized electrolyzer technology being developed at Savannah River National Laboratory with silicon carbide bayonet decomposition reactor technology being developed at Sandia National Laboratories. Both are part of the US DOE Nuclear Hydrogen Initiative. The flowsheet otherwise uses only proven chemical process components. Electrolyzer product is concentrated from 50 wt% sulfuric acid to 75 wt% via recuperative vacuum distillation. Pinch analysis is used to predict the high-temperature heat requirement for sulfuric acid decomposition. An Aspen Plus? model of the flowsheet indicates 340.3 kJ high-temperature heat, 75.5 kJ low-temperature heat, 1.31 kJ low-pressure steam, and 120.9 kJ electric power are consumed per mole of H₂ product, giving an LHV efficiency of 35.3% (41.7% HHV efficiency) if electric power is available at a conversion efficiency of 45%.     

Kinetic and thermodynamic analyses of mid/low-temperature ammonia decomposition in solar-driven hydrogen permeation membrane reactor

It is a promising method for hydrogen generation without carbon emitting by ammonia decomposition in a catalytic palladium membrane reactor driven by solar energy, which could also store and convert solar energy into chemical energy. In this study, kinetic and thermodynamic analyses of mid/low-temperature solar thermochemical ammonia decomposition for hydrogen generation in membrane reactor are conducted. Hydrogen permeation membrane reactor can separate the product and shift the reaction equilibrium forward for high conversion rate in a single step. The variation of conversion rate and thermodynamic efficiency with different characteristic parameters, such as reaction temperature (100–300 °C), tube length, and separation pressure (0.01–0.25 bar), are studied and analyzed. A near-complete conversion of ammonia decomposition is theoretically researched. The first-law thermodynamic efficiency, net solar-to-fuel efficiency, and exergy efficiency can reach as high as 86.86%, 40.08%, and 72.07%, respectively. The results of this study show the feasibility of integrating ammonia decomposition for hydrogen generation with mid/low-temperature solar thermal technologies.     

Solar chemical reactor technology for industrial production of lime

We developed the solar chemical reactor technology to effect the endothermic calcination reaction CaCO₃(s) → CaO(s) + CO₂(g) at 1200–1400 K. The indirect heating 10 kW_th multi-tube rotary kiln prototype processed 1–5 mm limestone particles, producing high purity lime that is not contaminated with combustion by-products. The quality of the solar produced quicklime meets highest industrial standards in terms of reactivity (low, medium, and high) and degree of calcination (exceeding 98%). The reactor’s efficiency, defined as the enthalpy of the calcination reaction at ambient temperature (3184 kJ kg⁻¹) divided by the solar energy input, reached 30–35% for quicklime production rates up to 4 kg h⁻¹. The solar lime reactor prototype operated reliably for more than 100 h at solar flux inputs of about 2000 kW m⁻², withstanding the thermal shocks that occur in solar high temperature applications. By substituting concentrated solar energy for fossil fuels as the source of process heat, one can reduce by 20% the CO₂ emissions in a state-of-the-art lime plant and by 40% in a conventional cement plant. The cost of solar lime produced in a 20 MW_th industrial solar calcination plant is estimated in the range 131–158 $/t, i.e. about 2–3 times the current selling price of conventional lime.     

Exergy analysis of a simulation of the sulfuric acid decomposition process of the SI cycle for nuclear hydrogen production

This article details comprehensive energy and exergy analyses of the sulfuric acid decomposition process of the sulfur–iodine (SI) thermochemical cycle for hydrogen production. Energy and exergy efficiencies of the proposed process were evaluated over a variety of reaction temperatures and pressures. At an atmospheric temperature of 25 °C, the calculated values of exergy destruction of the H₂SO₄ decomposer ranged between 157 kJ/mol and 360 kJ/mol over reaction temperatures of 800–1000 °C and pressures between 1 and 50 atm. It was shown that the exergy efficiency of the H₂SO₄ decomposer improved with an increase in reaction temperature, while reaction pressure had a negative effect on exergy efficiency.     

Hydrothermal synthesis of CuV2O6 supported on mesoporous SiO2 as SO3 decomposition catalysts for solar thermochemical hydrogen production

Hydrothermal synthesis of CuV₂O₆ supported on 3-D ordered mesoporous SiO₂ (CuV/SiO₂) was studied to evaluate the catalytic activity for SO₃ decomposition, which is a key step in solar thermochemical hydrogen production. A composite oxide hydrate, Cu₃O(V₂O₇)·H₂O, and an oxide hydroxide hydrate, Cu₃(OH)₂V₂O₇·(H₂O)₂, were formed at lower hydrothermal temperatures (≤200 °C). The oxide hydrate phase mainly yielded Cu₂V₂O₇ after calcination at 600 °C in air. By contrast, the hydrothermal synthesis at 250 °C (CuV/SiO₂@250) directly crystallized CuV₂O₆ from the oxide hydroxide hydrate, although its very large particle size (∼5 μm) is not suitable for the catalytic application. The SO₃ decomposition activity measured at 600 °C was associated with the yield as well as the dispersion of CuV₂O₆, giving rise to the maximum for the hydrothermal synthesis at 200 °C. CuV/SiO₂@250 achieved the highest catalytic activity at the reaction temperature of 650 °C, because the melting phase of CuV₂O₆ penetrated mesoporous SiO₂ and thus improved the dispersion of the active phase.     

Design of direct solar PV driven air conditioner

Solar air conditioning system directly driven by stand-alone solar PV is studied. The air conditioning system will suffer from loss of power if the solar PV power generation is not high enough. It requires a proper system design to match the power consumption of air conditioning system with a proper PV size. Six solar air conditioners with different sizes of PV panel and air conditioners were built and tested outdoors to experimentally investigate the running probabilities of air conditioning at various solar irradiations. It is shown that the instantaneous operation probability (OPB) and the runtime fraction (R_F) of the air conditioner are mainly affected by the design parameter r_pL (ratio of maximum PV power to load power). The measured OPB is found to be greater than 0.98 at instantaneous solar irradiation I_T > 600 W m⁻² if r_pL > 1.71. R_F approaches 1.0 (the air conditioner is run in 100% with solar power) at daily-total solar radiation higher than 13 MJ m⁻² day⁻¹, if r_pL > 3.     

Kinetic studies of sulfuric acid decomposition over Al–Fe2O3 catalyst in the sulfur-iodine cycle for hydrogen production

The decomposition of H₂SO₄ to produce SO₂ is the reaction with the highest energy demand in the sulfur-iodine cycle and it shows a large kinetic barrier. In the present study, alumina supported iron (III) oxide has been chosen for a detailed kinetic study. Experiments were carried out in the temperature range of 1023 K–1173 K using space hour velocities in the range of 0.146–0.731 kmol/kg-h in a quartz tube double stage continuous flow fixed bed reactor with 98% sulfuric acid feed over alumina supported Fe₂O₃ catalyst, nitrogen as inert carrier gas. From the homogeneous kinetic analysis, the apparent activation energy (E_A) was found to be 138.6 kJ/mol. This high activation energy indicates that the experiments were conducted in a kinetic controlled regime. The catalyst was well characterized by XRD, BET, TPR/TPO, SEM and FT-IR before and after reaction.     

Numerical modelling for the solar driven bi-reforming of methane for the production of syngas in a solar thermochemical micro-packed bed reactor

High temperature heat transfer and thermochemical storage performances of the solar driven bi-reforming of methane (SDSCB-RM) in a solar thermochemical micro-packed bed (ST-μPB) reactor are numerically investigated under different operating conditions along ST-μPB reactor length. A pseudo-homogeneous mathematical model is developed to simulate the heat and mass transfer processes coupled with thermochemical reaction kinetics in ST-μPB reactor with radiative heat loss. The effect of several parameters including the gas flow rate (Q_g), effective thermal conductivity (λ_s,eff), operating time (t_i) and operating temperature (T_op.) were investigated. The simulated results shown that the pressure drop increases with the increase of Q_g. When the Q_g is increased, the temperature profiles at the surface of the solid phase as well as the temperature profiles of the gas phase are remarkably decreasing. The consumption of reactants (CH₄, H₂O and CO₂) is increased when the λ_s,eff is gradually increased. On the other hand, the production of products (H₂, and CO) is remarkably increasing with the increase of the λ_s,eff. According to simulated results, the overall conversions of reactants (CH₄ and CO₂) and the dimensionless flow rate (DFR) of H₂ reach the maximum values of 98.18%, 75.61% and 1.6278 at the operating time of 2.50 h. The thermochemical energy storage efficiency (η_Chem) remarkably increases with the operating temperature and the maximum value of the η_Chem can be as high as 74.21% at 1123 K. The overall conversions of reactants (CH₄ and CO₂), DFR of H₂ and the energy stored as chemical enthalpy (Q_Chem) were also evaluated in relation to the operating temperature and their maximum values of 99.43%, 89.03%, 1.6383 and 1.3745 kJ/s are obtained at 1225 K.     

CO2 gasification of coal cokes using internally circulating fluidized bed reactor by concentrated Xe-light irradiation for solar gasification

For the solar thermochemical gasification of coal coke to produce CO + H₂ synthetic gas using concentrated solar radiation, a windowed reactor prototype is tested and demonstrated at laboratory scale for CO₂ gasification of coal coke using concentrated Xe light from a 3-kW_th sun simulator. The reactor was designed to be combined with a solar reflective tower or beam-down optics. The results for gasification performance (CO production rate, carbon conversion, and light-to-chemical efficiency) are shown for various CO₂ flow rates and ratios. A kinetics analysis based on homogeneous and shrinking core models and the temperature distributions of the prototype particle bed are compared with those for a conventional fluidized bed reactor tested under the same Xe light irradiation and CO₂ flow-rate conditions. The effectiveness and potential impacts of internally circulating fluidized bed reactors for enhancing gasification performance levels and inducing consistently higher bed temperatures are discussed in this paper.     

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%.     

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.     

Performance assessment of thermochemical CO2/H2O splitting in moving bed and fluidized bed reactors

In this paper, we present the assessment of moving bed reactors and fluidized bed reactors operating in different fluidizing regimes for solar thermochemical redox cycles (STRC) for syngas production. The reduction reactor with a moving bed (MB_RED) while the oxidation reactor (OXI) is either a moving bed reactor (MB_OXI) or bubbling bed (BB_OXI) yields higher performance. It was observed that only water splitting is suitable at 1400 °C and 10⁻³ bar reduction conditions. The higher reduction temperature and pressure improved the efficiency of the CO₂/H₂O splitting unit. The requirement of the H₂/CO ratio drives the gas feed (CO₂/H₂O) into OXI. To achieve an H₂/CO ratio of 1, MB_OXI and BB_OXI require an equimolar mixture of CO₂ and H₂O at 1600 °C. However, to achieve a similar H₂/CO ratio at a lower temperature of 1500 °C, the gas feed of the CO₂/H₂O ratio required is 3. A similar H₂/CO ratio is achieved for OXI operating in a turbulent and fast fluidizing, but the selectivity is lower due to lower reaction rates. OXI as a transport bed is least suited based on solid conversion (X_OXI), H₂/CO, or efficiency. The results are useful in designing the redox reactors for syngas.     

A review of catalytic sulfur (VI) oxide decomposition experiments

Sulfur (VI) oxide, also known as sulfur trioxide or SO₃, decomposition is an oxygen-generating decomposition reaction that proceeds in the gaseous system SO₃/SO₂/O₂/H₂O at temperatures above 500 K. Maximum decomposition yield of SO₃ to SO₂ and O₂ is best achieved at temperatures of over 1000 K with an appropriate catalyst. According to the literature, noble metals and some transition metal oxides are highly effective catalysts in the laboratory environment. Sulfur (VI) oxide decomposition is the energetic and temperature limiting step of several endothermic hydrogen generating chemical process heat plants. In particular, the General Atomics Sulfur Iodine cycle and the Westinghouse Hybrid Sulfur cycle are candidates for thermal coupling to a high temperature nuclear reactor. Therefore the sulfur (VI) oxide decomposition reaction is a potential heat sink for a high temperature nuclear reactor. Thus, optimization of catalyst selection is required, both for operational efficiency and safety. In this paper, reaction mechanisms and catalyst composition for sulfur (VI) oxide decomposition are reviewed. Chemical kinetics data from previous sulfur (VI) oxide decomposition experiments are extracted from archival journal papers or other open literature. The available experimental database suggests that Pt-based catalysts have the highest stable activity among the noble metals and Fe₂O₃-based catalysts have the highest stable activity among the transition metal oxides. The decomposition temperature of the corresponding metal sulfate dictates the catalytic activity of a given transition metal oxide.     

Production of hydrogen from hydrogen sulfide assisted by dielectric barrier discharge

Hydrogen production by non-thermal plasma (NTP) assisted direct decomposition of hydrogen sulfide (H₂S) was carried out in a dielectric barrier discharge (DBD) reactor with stainless steel inner electrode and copper wire as the outer electrode. The specific advantage of the present process is the direct decomposition of H₂S in to H₂ and S and the novelty of the present study is the in-situ removal of sulfur that was achieved by operating DBD plasma reactor at ∼430 K. Optimization of various parameters like the gas residence time in the discharge, frequency, initial concentration of H₂S and temperature was done to achieve hydrogen production in an economically feasible manner. The typical results indicated that NTP is effective in dissociating H₂S into hydrogen and sulfur and it has been observed that by optimizing various parameters, it is possible to achieve H₂ production at 300 kJ/mol H₂ that corresponds to ∼3.1 eV/H₂, which is less than the energy demand during the steam methane reforming (354 kJ/mol H₂ or ∼3.7 eV/H₂).