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.     

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.     

Direct dimethyl ether (DME) synthesis through a thermally coupled heat exchanger reactor

Compared to some of the alternative fuel candidates such as methane, methanol and Fischer–Tropsch fuels, dimethyl ether (DME) seems to be a superior candidate for high-quality diesel fuel in near future. The direct synthesis of DME from syngas would be more economical and beneficial in comparison with the indirect process via methanol synthesis. Multifunctional auto-thermal reactors are novel concepts in process intensification. A promising field of applications for these concepts could be the coupling of endothermic and exothermic reactions in heat exchanger reactors. Consequently, in this study, a double integrated reactor for DME synthesis (by direct synthesis from syngas) and hydrogen production (by the cyclohexane dehydrogenation) is modelled based on the heat exchanger reactors concept and a steady-state heterogeneous one-dimensional mathematical model is developed. The corresponding results are compared with the available data for a pipe-shell fixed bed reactor for direct DME synthesis which is operating at the same feed conditions. In this novel configuration, DME production increases about 600 Ton/year. Also, the effects of some operational parameters such as feed flow rates and the inlet temperatures of exothermic and endothermic sections on reactor behaviour are investigated. The performance of the reactor needs to be proven experimentally and tested over a range of parameters under practical operating conditions.     

Plasma reforming for hydrogen production: Pathways,reactors and storage

Hydrogen is an energy carrier with a very high energy density (>119 MJ/kg). Pure hydrogen is barely available; thus, it requires extraction from its compounds. Steam reforming and water electrolysis are commercially viable technologies for hydrogen production from water, alcohols, methane, and other hydrocarbons; however, both processes are energy-intensive. Current study aims at understanding the methane and ethanol-water mixture pathway to generate hydrogen molecules. The various intermediate species (like CH_X, CH₂O, CH₃CHO) are generated before decomposing methane/ethanol into hydrogen radicals, which later combine to form hydrogen molecules. The study further discusses the various operating parameters involved in plasma reforming reactors. All the reactors work on the same principle, generating plasma to excite electrons for collision. The dielectric barrier discharge reactor can be operated with or without a catalyst; however, feed flow rate and discharge power are the most influencing parameters. In a pulsed plasma reactor, feed flow rate, electrode velocity, and gap are the main factors that can raise methane conversion (40–60%). While the gliding arc plasma reactor can generate up to 50% hydrogen yield at optimized values of oxygen/carbon ratio and residence time, the hydrogen yield in the microwave plasma reactor is affected by flow rate and feed concentration. Therefore, all the reactors have the potential to generate hydrogen at lower energy demand.     

Hydrogen production from solar thermal dissociation of natural gas: development of a 10 kW solar chemical reactor prototype

This study addresses the solar thermal decomposition of natural gas for the co-production of hydrogen, as well as Carbon Black as a high-value nano-material, with the bonus of zero CO₂ emissions. The work focused on the development of a medium-scale solar reactor (10 kW) based on the concept of indirect heating. The solar reactor is composed of a cubic cavity receiver (20 cm side), which absorbs concentrated solar irradiation through a quartz window via a 9 cm-diameter aperture. The reacting gas flows inside four graphite tubular reaction zones that are settled vertically inside the cavity. Experimental results were as follows: methane conversion and hydrogen yield of up to 98% and 90%, respectively, were achieved at 1770 K, and acetylene was the most important by-product, with a mole fraction up to about 5%. The effect of the methane mole fraction in the feed gas, the residence time and the temperature on the reaction extent was analyzed. In addition to the experimental section, thermal simulations were carried out. They showed a homogeneous temperature distribution inside the cavity receiver of the reactor and permit to draw up a thermal balance.     

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.     

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.     

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.     

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%.     

Modelling the hydrodynamics and kinetics of methane decomposition in catalytic liquid metal bubble reactors for hydrogen production

Bubble reactors using molten metal alloys (e.g, nickel-bismuth and copper-bismuth) with strong catalytic activity for methane decomposition are an emerging technology to lower the carbon intensity of hydrogen production. Methane decomposition occurs non-catalytically inside the bubbles and catalytically at the gas-liquid interface. The reactor performance is therefore affected by the hydrodynamics of bubble flow in molten metal, which determines the evolution of the bubble size distribution and of the gas holdup along the reactor height. A reactor model is first developed to rigorously account for the coupling of hydrodynamics with catalytic and non-catalytic reaction kinetics. The model is then validated with previously reported experimental data on methane decomposition at several temperatures in bubble columns containing a molten nickel-bismuth alloy. Next, the model is applied to optimize the design of multitubular catalytic bubble reactors at industrial scales. This involves minimizing the total liquid metal volume for various tube diameters, melt temperatures, and percent methane conversions at a specified hydrogen production rate. For example, an optimized reactor consisting of 891 tubes, each measuring 0.10 m in diameter and 2.11 m in height, filled with molten Ni_0·27Bi_0.73 at 1050 °C and fed with pure methane at 17.8 bar, may produce 10,000 Nm³.h^?1 of hydrogen with a methane conversion of 80% and a pressure drop of 1.6 bar. The tubes could be heated in a fired heater by burning either a fraction of the produced hydrogen, which would prevent CO₂ generation, or other less expensive fuels.     

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.     

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.     

Methane decomposition to produce COx-free hydrogen and nano-carbon over metal catalysts: A review

Catalytic decomposition of methane (CDM) is a promising technology for producing CO_x-free hydrogen and nano-carbon, meanwhile it is a prospective substitute to steam reforming of methane for producing hydrogen. The produced hydrogen is refined and can be applied to the field of electronic, metallurgical, synthesis of fine organic chemicals and aerospace industries. However, the CDM for CO_x-free hydrogen production is still in its infancy. The urgent for industrial scale of CDM is more important than ever in the current situation of huge CO_x emission. This review studies CDM development on Ni-based, noble metal, carbon and Fe-based catalysts, especially over cheap Fe-based catalyst to indicate that CDM would be a promising feasible method for large hydrogen production at a moderate cheap price. Besides, the recent advances in the reaction mechanism and kinetic study over metal catalysts are outlined to indicate that the catalyst deactivation rate would become more quickly with increasing temperature than the CDM rate does. This review also evaluates the roles played by various parameters on CDM catalysts performance, such as metal loading effect, influences of supports, hydrogen reduction, methane reduction and methane/hydrogen carburization. Catalysts deactivation by carbon deposition is the prime challenge found in CDM process, as an interesting approach, a molten-metal reactor to continually remove the floated surface solid carbons is put forwarded in accordance to overcome the deactivation drawback. Moreover, particular CDM reactors using substituted heating sources such as plasma and solar are detailed illustrated in this review in addition to the common electrical heating reactors of fixed bed, fluidized bed reactors. The development of high efficiency catalysts and the optimization of reactors are necessary premises for the industrial-scale production of CDM.     

Decreasing methane production in hydrogenogenic UASB reactors fed with cheese whey

One of the problems in fermentative hydrogen producing reactors, inoculated with pre-treated anaerobic granular sludge, is the eventual methane production by hydrogen-consuming methanogens. In this study, strategies such as reduction of pH and HRT, organic shock loads and repeated biomass heat treatment were applied to hydrogenogenic UASB reactors fed with cheese whey, that showed methane production after certain time of continuous operation (between 10 and 60 days). The reduction of pH to 4.5 not only decreased methane production but also hydrogen production. Organic shock load (from 20 to 30 g COD/L-d) was the more effective strategy to decrease the methane production rate (75%) and to increase the hydrogen production rate (172%), without stopping reactor operation. Repeated heat treatment of the granular sludge was the only strategy that inhibited completely methane production, leading to high volumetric hydrogen production rates (1.67 L H₂/L-d), however this strategy required stopping reactor operation; in addition homoacetogenesis, another hydrogen-consuming pathway, was not completely inhibited. This work demonstrated that it was possible to control the methane activity in hydrogen producing reactors using operational strategies.     

Solar test of an integrated sodium reflux heat pipe receiver/reactor for thermochemical energy transport

A chemical reactor for carbon dioxide reforming of methane was integrated into a sodium reflux heat pipe receiver and tested in the solar furnace of the Weizmann Institute of Science, Rehovot, Israel. The receiver/reactor was a heat pipe with seven tubes inside an evacuated metal box containing sodium. The catalyst, 0.5 wt% Rh on alumina, filled two of the tubes with the front surface of the box serving as the solar absorber. In operation, concentrated sunlight heated the front plate and vaporized sodium from a wire mesh wick attached to the other side. Sodium vapor condensed on the reactor tubes, releasing latent heat and returning to the wick by gravity. The receiver system performed satisfactorily in many tests under varying flow conditions. The maximum power absorbed was 7.5 kW at temperatures above 800°C. The feasibility of operating a heat pipe receiver/reactor under solar conditions was proven, and the advantages of reflux devices confirmed.     

Enhanced hydrogen production in a UASB reactor by retaining microbial consortium onto carbon nanotubes (CNTs)

Biohydrogen and subsequent biomethane generation from biomass is a promising strategy for renewable energy supply, because this combination can lead to higher energy recovery efficiency and faster fermentation than single methane fermentation. Microbial consortium control by retaining hydrogen-producers through the addition of microbial carriers is an alternative to constructing hydrogen-producing reactors. Here we report the use of carbon nanotubes (CNTs) as microbial carriers to enhance microbial retention and the production of biohydrogen. Laboratory-scale upflow anaerobic sludge blanket (UASB) reactors with CNTs at 100 mg/L achieved a maximal hydrogen production rate of 5.55 L/L/d and a maximal hydrogen yield of 2.45 mol/mol glucose. Compared to frequently used activated carbon (AC) particles, CNTs resulted in quicker startup and better performance of hydrogen fermentation in UASB reactors. Scanning electron microscopy (SEM) and pyrosequencing results revealed that the reactor with CNTs led to a high proportion of hydrogen-producing bacteria among the microbial consortium, which endowed the microbes with strong flocculation capacity and hydrogen productivity.     

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.     

Membrane bubble column reactor model for the production of hydrogen by methane pyrolysis

A membrane reactor model is developed to describe, model, and design molten metal methane pyrolysis bubble column reactors. It is utilized to demonstrate that a membrane reactor allows conversions in excess of the equilibrium conversion implied by the feed and operating conditions. Ultra-high conversion eliminates the need to separate product hydrogen from unreacted methane, thereby eliminating the need to recycle un-reacted methane and reducing the total equipment sizes and energy costs. Furthermore, it is shown that the hydrogen can be completely removed through the membrane reactor walls before the gas bubbles breakthrough the molten metal layer into the reactor headspace. The equations also apply to non-membrane reactors, and are therefore useful for future general conceptual design studies. The general applicability is demonstrated by comparison of the model predictions to published experimental data on methane pyrolysis in a non-membrane bubble column reactor.     

Modeling & optimization of renewable hydrogen production from biomass via anaerobic digestion & dry reformation

There is a growing interest in the usage of hydrogen as an environmentally cleaner form of energy for end users. However, hydrogen does not occur naturally and needs to be produced through energy intensive processes, such as steam reformation. In order to be truly renewable, hydrogen must be produced through processes that do not lead to direct or indirect carbon dioxide emissions. Dry reformation of methane is a route that consumes carbon dioxide to produce hydrogen. This work describes the production of hydrogen from biomass via anaerobic digestion of waste biomass and dry reformation of biogas. This process consumes carbon dioxide instead of releasing it and uses only renewable feed materials for hydrogen production. An end-to-end simulation of this process is developed primarily using Aspen HYSYS® and consists of steady state models for anaerobic digestion of biomass, dry reformation of biogas in a fixed-bed catalytic reactor containing Ni–Co/Al₂O₃ catalyst, and a custom-model for hydrogen separation using a hollow fibre membrane separator. A mixture-process variable design is used to simultaneously optimize feed composition and process conditions for the process. It is identified that if biogas containing 52 mol% methane, 38 mol% carbon dioxide, and 10 mol% water (or steam) is used for hydrogen production by dry reformation at a temperature of 837.5 °C and a pressure of 101.3 kPa; optimal values of 89.9% methane conversion, 99.99% carbon dioxide conversion and hydrogen selectivity 1.21 can be obtained.