Radiative transfer in a solar chemical reactor for the co-production of hydrogen and carbon by thermal decomposition of methane

Radiation heat transfer in a solar chemical reactor for the co-production of hydrogen and carbon by thermal decomposition of CH₄ is analyzed by the Monte Carlo ray-tracing method. The solar chemical reactor features a vortex flow of CH₄ confined to a cavity and laden with carbon particles that serve simultaneously as radiant absorbers and nucleation sites for the heterogeneous decomposition reaction. The reactor is treated as a 3D non-isothermal non-gray absorbing-emitting-scattering gas/particle suspension directly exposed to concentrated solar irradiation. The analysis includes coupling to conduction/convection heat transfer and chemical kinetics. Calculated temperature distribution and chemical conversion are compared with the experimentally measured values obtained with a 5 kW prototype reactor tested in a solar furnace.     

Computational Fluid Dynamics of Co-Production of Zinc and Syngas in a Solar Reactor

In this paper, the production of Zn and H₂ in a 4 kW solar reactor has been investigated. Utilization of a renewable energy source increases the importance of this work. The effect of changes in reactor geometry was analyzed, and, with changing different parameters, their effects were investigated. At constant thermal energy rate, with increasing CH₄ inlet gas flow rate there is a decrease in reaction chamber temperature and therefore in reactor efficiency. Increasing rotation of reaction chamber causes its temperature to increase, where an increase of 150% in rotation caused a 1% increase in efficiency. With the increase in thermal energy rate, thermal efficiency was increased. Also, with increasing rate of thermal energy, the rate of chemical reaction that produces Zn and H₂ increased. The geometry used in the light beams concentrator section causes the occurrence of maximum temperature in the desired point (cylindrical chamber) which increases system efficiency significantly.     

Catalytic Ammonia Decomposition Over Fe/Fe4N

The catalytic ammonia decomposition over iron and iron nitride, Fe₄N, under the atmosphere of ammonia–hydrogen mixtures of different amounts of ammonia in the temperature range of 400–550 °C by means of thermogravimetry has been studied. A differential tubular reactor with mixing has been used. The ammonia concentration in the gas phase during all the process was analysed. The balance between the inlet and outlet ammonia quantity has been used to determine a degree of ammonia conversion and the values of decomposition reaction rate. The activation energy of ammonia decomposition reaction over Fe and Fe₄N was found to be 68 and 143 kJ/mol, respectively.     

Steam gasification of an australian bituminous coal in a fluidized bed

To produce low calorific value gas, Australian coal has been gasified with air and steam in a fluidized bed reactor (0.1 m-I.Dx1.6 m-high) at atmospheric pressure. The effects of fluidizing gas velocity (2–5 U_f/U_mf), reaction temperature (750–900 °C), air/coal ratio (1.6-3.2), and steam/coal ratio (0.63–1.26) on gas composition, gas yield, gas calorific value of the product gas and carbon conversion have been determined. The calorific value and yield of the product gas, cold gas efficiency, and carbon conversion increase with increasing fluidization gas velocity and reaction temperature. With increasing air/coal ratio, carbon conversion, cold gas efficiency and yield of the product gas increase, but the calorific value of the product gas decreases. When steam/coal ratio is increased, cold gas efficiency, yield and calorific value of the product gas increase, but carbon conversion is little changed. Unburned carbon fraction of cyclone fine decreases with increasing fluidization gas velocity, reaction temperature and air/coal ratio, but is nearly constant with increasing steam/coal ratio. Overall carbon conversion decreases with increasing fluidization velocity and air/ coal ratio, but increases with increasing reaction temperature. The particle entrainment rate increases with increasing fluidization velocity, but decreases with increasing reaction temperature. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Water Gas Shift Reaction in a Membrane Reactor Using a High Hydrogen Permselective Silica Membrane

A membrane reactor (MR) for the water gas shift (WGS) reaction was developed by integrating a highly hydrogen permselective silica membrane. The membrane was prepared using an extended counter-diffusion chemical vapor deposition (CVD) method. A tetramethylorthosilicate (TMOS) silica source was fed from one side of the membrane support and oxygen gas fed from the other. The dense silica film was deposited on a porous support by pressurizing the side that TMOS is supplied. A high hydrogen permselective silica membrane was obtained by this method. A commercial Pt catalyst was used in the WGS reaction. Efficacy of the silica membrane toward the WGS reaction was investigated as a function of temperature (523-623 K), steam/carbon monoxide (S/C) ratio (1-3), differential pressure (0-100 kPa), and gas hourly space velocity (GHSV; 1800-5400 h^?1). The CO conversion in the MR was higher than that for a fixed bed reactor (FBR) under all experimental conditions, and was also higher than the thermodynamic equilibrium conversion under almost all experimental conditions. This was due to the selective abstraction of hydrogen from the product stream by the silica membrane. At an S/C of 1.0, the CO conversion in the MR was superior to that in a FBR by 16.8%.     

Biodiesel production from waste cooking palm oil using calcium oxide supported on activated carbon as catalyst in a fixed bed reactor

A reactor has been developed to produce high quality fatty acid methyl esters (FAME) from waste cooking palm oil (WCO). Continuous transesterification of free fatty acids (FFA) from acidified oil with methanol was carried out using a calcium oxide supported on activated carbon (CaO/AC) as a heterogeneous solid-base catalyst. CaO/AC was prepared according to the conventional incipient-wetness impregnation of aqueous solutions of calcium nitrate (Ca(NO₃)₂·4H₂O) precursors on an activated carbon support from palm shell in a fixed bed reactor with an external diameter of 60 mm and a height of 345 mm. Methanol/oil molar ratio, feed flow rate, catalyst bed height and reaction temperature were evaluated to obtain optimum reaction conditions. The results showed that the FFA conversion increased with increases in alcohol/oil molar ratio, catalyst bed height and temperature, whereas decreased with flow rate and initial water content in feedstock increase. The yield of FAME achieved 94% at the reaction temperature 60 °C, methanol/oil molar ratio of 25: 1 and residence time of 8 h. The physical and chemical properties of the produced methyl ester were determined and compared with the standard specifications. The characteristics of the product under the optimum condition were within the ASTM standard. High quality waste cooking palm oil methyl ester was produced by combination of heterogeneous alkali transesterification and separation processes in a fixed bed reactor. In sum, activated carbon shows potential for transesterification of FFA.     

ON THE EFFECTS OF SYNGAS COMPOSITION AND WATER-GAS-SHIFT REACTION RATE ON FT SYNTHESIS OVER IRON BASED CATALYST IN A SLURRY REACTOR

Water gas shift reaction plays an important role in the Fischer-Tropsch synthesis reaction over iron-based catalysts. A slurry reactor model which accounted for the kinetics of both Fischer-Tropsch synthesis and water gas shift reaction was used to investigate the effects of hydrogen to carbon monoxide ratio, water vapor concentration and reactor temperature on synthesis gas conversion. The model was used to determine optimum concentration of water in the feed gas. For a given reactor temperature, the optimum concentration of water in the feed gas was found to increase with decreasing hydrogen to carbon monoxide ratio. The optimum concentration of water in the feed gas was found to decrease with increasing reactor temperature. Increasing the water gas shift reaction rate improved syngas conversion for low reaction temperatures.     

Non‐Isothermal Non‐Adiabatic Dehydrogenation of Cyclohexane in Catalytic Membrane Reactors

Abstract

This study focuses on modeling and analysis of the non‐isothermal, non‐adiabatic, dehydrogenation of cyclohexane in membrane catalytic reactors. The dehydrogenation reaction is endothermic with a low equilibrium conversion of 0.06 at a temperature of 473 K and pressure of 101 kPa. The membrane reactor removes hydrogen from the reaction mixture and results in increase of the reaction conversion. The analysis is made as a function of feed flow rate, feed temperature, feed composition, inert flow rate in the feed stream, flow rate of sweep gas, pressures of the tube side and shell side, permeability constant of hydrogen, and tube diameter. The analysis also includes a study of the co‐current and the counter‐current flow modes. The results show lower conversion for the counter‐current flow mode, because of the decrease in the driving force for permeation. A comparison of model predictions against previous literature studies shows good agreement.     

Design and simulation of a solar chemical reactor for the thermal reduction of metal oxides: Case study of zinc oxide dissociation

A laboratory-scale solar reactor was designed and simulated for the thermal reduction of metal oxides involved in water-splitting thermochemical cycles for hydrogen production. This reactor features a cavity-receiver directly heated by concentrated solar energy, in which solid particles are continuously injected. A computational model was developed by coupling the fluid flow, heat and mass transfer, and the chemical reaction. The reactive particle-laden flow was simulated, accounting for a multiphase model (solid-gas flow). A discrete phase model based on a Lagrangian approach was developed. The kinetics of the chemical reaction was considered in the specific case of zinc oxide dissociation for which reliable data are available. The complete model predicts temperature and gas velocity distributions, species concentration profiles inside the reactor, particle trajectories and fates, and conversion rate assessing the reaction degree of completion. The reaction extent is highly dependent on temperature of the radiation-absorbing particles. Initial diameter of injected particles is also a key parameter because it determines the available surface area for a given particle mass feed rate. The higher the particle surface area, the higher the conversion rate. As a result, reaction completion can be achieved when particle temperature exceeds 2200 K for a initial particle diameter.     

松木屑与废橡胶化学链共气化特性试验

在自行设计的两级固定床反应器上,对以天然贫铁矿石为载氧体的松木屑与废橡胶化学链共气化特性进行了研究。考察了载氧体的存在、废橡胶掺混比例、一级反应器温度、水蒸气流量等因素对生物质化学链共气化过程的影响。结果表明：载氧体的存在能显著改善气化效果;掺混一定量的废橡胶可以显著提高低位热值和碳转化率,并且呈现协同效应。本试验中最佳的废橡胶掺混比例为20%;共气化过程中的产气率、碳转化率均随温度的增加（750～950℃）而逐渐升高,但热值随温度的升高而有所下降;水蒸气流量的增加能显著提高合成气中H₂的含量,进水流量保持在0.66g/min时,能实现生物质共气化过程产气率、碳转化率、低位热值等各项指标的最佳平衡。通过扫描电镜（SEM）、X射线衍射（XRD）等表征分析,发现天然贫铁矿石在长时间运行中表现良好的反应性和耐磨损性。     

Reactivity of a spray-dried NiO/NiAl2O4 oxygen carrier for chemical-looping combustion

Kinetic data of a promising oxygen carrier of NiO/NiAl₂O₄ have been established from experiments in a small fluidized bed batch reactor using methane. The particles were prepared by spray-drying using commercially available raw material and selected as the best candidates from an earlier screening study. The particles clearly showed high reactivity, with a maximum gas yield between 86% and 93% in the temperature interval 750 °C to 950 °C when using a bed mass and a gas flow corresponding to only 6 kg/MW_fuel. A comparison of the reactivity with data from TGA experiments showed that the reactivity generally was faster in the batch fluidized bed in the investigated temperature interval. A simple reactor model using kinetic data from the batch fluidized bed reactor and the TGA predicted a minimum mass of 9–24 kg/MW_fuel of oxygen carrier particles for full gas yield of methane to carbon dioxide in the fuel reactor. Comparison with experiments performed in a 10 and 120 kW CLC reactor with the same type of oxygen carrier showed that even when employing 13 to 50 times the amount of oxygen carrier theoretically needed for complete gas conversion, full gas yield was not obtained in the circulating systems. Hence it is of great importance to consider the fluid dynamics and gas-solid contact when modeling the fuel reactor of a chemical-looping combustor.     

A novel dual circulating fluidized bed system for chemical looping processes

A fluidized bed system combining two circulating fluidized bed reactors is proposed and investigated for chemical looping combustion. Direct hydraulic communication of the two circulating fluidized bed reactors via a fluidized loop seal allows for high rates of global solids circulation and results in a stable solids distribution in the system. A 120 kW fuel power bench scale unit was designed, built, and operated. Experimental results are presented for natural gas as fuel using a nickel‐based oxygen carrier. No carbon was lost to the air reactor under any conditions operated. It is shown from fuel power variations that a turbulent/fast fluidized bed regime in the fuel reactor is advantageous. Despite the relatively low riser heights (air reactor: 4.1 m, fuel reactor: 3.0 m), high CH₄ conversion and CO₂ yield of up to 98% and 94%, respectively, can be reported for the material tested. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Measurement of intrinsic rates for homogeneous gas‐phase reactions at high temperatures

A coiled quartz tubular reactor has been designed to measure the intrinsic reaction kinetics for homogeneous reactions at high temperatures up to 1100°C. Actual gas residence times were less than 100 ms. A simple and well‐studied test reaction (i.e., the decomposition of nitrous oxide, N₂O), with published intrinsic kinetics, was used to verify the operation of the experimental reactor. For this system, Peclet numbers (Pe = uL/DL) computed from experimental conversion data were greater than 1000, indicating that the plug flow assumption could be used with this reactor system to determine intrinsic rate expressions with errors of less than 5% for the conditions studied.     

Theoretical and experimental basics of the formation of optimal catalyst layers in tubular reactors

Results from research on the structure of a catalyst’s granular bed are presented. The influence on catalytic reactions is estimated and the industrial use of the obtained results in tubular reactors of natural gas steam conversion is demonstrated. The influence of methods for loading catalyst particles on the spatial distribution of the porosity and filterable flow in a fixed bed of a tubular reactor tube is proved theoretically and experimentally. The possibility of the method of loading influencing the process technological parameters is demonstrated via the example of the commercially important reaction of natural gas conversion by steam. It was shown in particular that the correct loading of a bed can lower the temperature of the external walls of steam conversion reactor tubes by several tens of degrees. This ensures a longer service life for tubes operating at 700–1000°C. A loading device was designed on the basis of the obtained results and has been used to load Russia’s largest reactors for the conversion of natural gas by steam in M-750 units of methanol production in Tomsk and Gubakha.     

PEM – Fuel Cell System for Residential Applications

Viessmann is developing a PEM fuel cell system for residential applications. The uncharged PEM fuel cell system has a 2 kW electrical and 3 kW thermal power output. The Viessmann Fuel Processor is characterized by a steam‐reformer/burner combination in which the burner supplies the required heat to the steam reformer unit and the burner exhaust gas is used to heat water. Natural gas is used as fuel, which is fed into the reforming reactor after passing an integrated desulphurisation unit. The low temperature (600 °C) fuel processor is designed on the basis of steam reforming technology. For carbon monoxide removal, a single shift reactor and selective methanisation is used with noble metal catalysts on monoliths. In the shift reactor, carbon monoxide is converted into hydrogen by the water gas shift reaction. The low level of carbon monoxide at the outlet of the shift reactor is further reduced, to approximately 20 ppm, downstream in the methanisation reactor, to meet PEM fuel cell requirements. Since both catalysts work at the same temperature (240 °C), there is no requirement for an additional heat exchanger in the fuel processor. Start up time is less than 30 min. In addition, Viessmann has developed a 2 kW class PEFC stack, without humidification. Reformate and dry air are fed straight to the stack. Due to the dry operation, water produced by the cell reaction rapidly diffuses through the electrolyte membrane. This was achieved by optimising the MEA, the gas flow pattern and the operating conditions. The cathode is operated by an air blower.     

基于赤铁矿载氧体的煤化学链燃烧试验

化学链燃烧是一种具有CO₂内分离特性的燃烧方式。以赤铁矿为载氧体,在1 kW_th级串行流化床上进行了煤化学链燃烧试验。讨论了燃料反应器温度对气体产物组分的影响;比较了各反应参数对煤气化效率、煤气化产物的转化效率及碳捕集效率的影响情况,分析了煤中硫的排放问题。试验结果表明：温度由900℃升高到985℃,燃料反应器中CO体积份额逐渐增加,CO₂体积份额逐渐减小,空气反应器中CO₂浓度呈线性下降。燃料反应器温度的升高促进煤气化效率及碳捕集效率大大提高。载氧体量和系统负荷是煤气化产物转化效率的主要影响因素,载氧体量的增加和负荷的增加分别会使煤气化产物转化效率提高和下降。燃料反应器中的硫主要以SO₂形式存在于燃料反应器,随温度的升高,SO₂浓度由515×10^-6逐渐增加到562×10^-6相似文献   

Microchannel Autothermal Reforming of Methane to Synthesis Gas

Autothermal reforming of methane to synthesis gas (CO and H₂) is studied in a microchannel reactor comprised of Pt- and Rh-based catalysts that are coated on opposite walls of the channel. The effects of operating parameters and microchannel catalyst configuration on methane conversion and CO selectivity are analyzed. The parameters considered are the residence time of the reactants (12.9–25.7 ms), reaction temperature (500–650 °C), molar steam-to-carbon (S/C = 0–3.0) and oxygen-to-carbon (O₂/C = 0.47–0.63) ratios at the inlet. Doubling the residence time leads to ca. 10 % increase in methane conversion, but has only a 4 % contribution to the CO selectivity. Higher O₂/C ratios improve extent of methane oxidation, but reduce selectivity due to CO₂ production. When the temperature is raised from 500 to 650 °C, conversion increases from 12.8 to 46.6 % and selectivity increases from 20.1 to 35.7 %. S/C ratio has the greatest effect on the outlet H₂/CO ratio, which is found to vary between 0.93 and 2.68, via the water–gas shift reaction. Comparison of the present catalyst configuration with the use of bimetallic Pt–Rh coating in the microchannel under identical conditions shows that the latter can improve conversion by 20 % and CO selectivity by 33 %.     

A Novel Process for Renewable Methane Production: Combining Direct Air Capture by K<Subscript>2</Subscript>CO<Subscript>3</Subscript>/Alumina Sorbent with CO<Subscript>2</Subscript> Methanation over Ru/Alumina Catalyst

CO₂ methanation over supported ruthenium catalysts is considered to be a promising process for carbon capture and utilization and power-to-gas technologies. In this work 4% Ru/Al₂O₃ catalyst was synthesized by impregnation of the support with an aqueous solution of Ru(OH)Cl₃, followed by liquid phase reduction using NaBH₄ and gas phase activation using the stoichiometric mixture of CO₂ and H₂ (1:4). Kinetics of CO₂ methanation reaction over the Ru/Al₂O₃ catalyst was studied in a perfectly mixed reactor at temperatures from 200 to 300 °C. The results showed that dependence of the specific activity of the catalyst on temperature followed the Arrhenius law. CO₂ conversion to methane was shown to depend on temperature, water vapor pressure and CO₂:H₂ ratio in the gas mixture. The Ru/Al₂O₃ catalyst was later tested together with the K₂CO₃/Al₂O₃ composite sorbent in the novel direct air capture/methanation process, which combined in one reactor consecutive steps of CO₂ adsorption from the air at room temperature and CO₂ desorption/methanation in H₂ flow at 300 or 350 °C. It was demonstrated that the amount of desorbed CO₂ was practically the same for both temperatures used, while the total conversion of carbon dioxide to methane was 94.2–94.6% at 300 °C and 96.1–96.5% at 350 °C.     

CO Oxidation Activity of Ag/TiO2 Catalysts Prepared via Oxalate Co-precipitation

Ag/TiO₂ catalysts with different Ag loadings (2, 4, 7 and 10% (w/w)) have been prepared by means of co-precipitation of Ag- and TiO-oxalates followed by temperature programmed oxidation (TPO). The catalysts were subjected to CO oxidation in a flow reactor at atmospheric pressure and temperatures up to 573 K. Best conversion performance was obtained in a CO/O₂ = 1:1 mixture over 10% Ag/TiO₂ for which the temperature of 50% CO conversion was T ₅₀ = 333 K. The initial reaction rates were determined in a circulation reactor at low conversions and apparent activation energies between 13 and 25 kJ/mol were found for all catalysts. Transmission electron microscopy shows a broad range of nano-sized Ag particles on TiO₂ (nearly pure anatase).     

Mechanisms and kinetics of homogeneous secondary reactions of tar from continuous pyrolysis of wood chips

The change of mass and composition of biomass tar due to homogeneous secondary reactions was experimentally studied by means of a lab reactor system that allows the spatially separated production and conversion of biomass tar. A tarry pyrolysis gas was continuously produced by pyrolysis of wood chips (fir and spruce, 10-40 mm diameter) under fixed-bed biomass gasification conditions. Homogeneous secondary tar reactions without the external supply of oxidising agents were studied in a tubular flow reactor operated at temperatures from 500 to 1000 °C and with space times below 0.2 s. Extensive chemical analysis of wet chemical tar samples provided quantitative data about the mass and composition of biomass tar during homogeneous conversion. These data were used to study the kinetics of the conversion of gravimetric tar and the formation of PAH compounds, like naphthalene.It is shown that, under the reaction conditions chosen for the experiments, homogeneous secondary tar reactions become important at temperatures higher than 650 °C, which is indicated by the increasing concentrations of the gases CO, CH₄, and H₂ in the pyrolysis gas. The gravimetric tar yield decreases with increasing reactor temperatures during homogeneous tar conversion. The highest conversion reached in the experiments was 88% at a reference temperature of 990 °C and isothermal space time of 0.12 s. Hydrogen is a good indicator for reactions that convert the primary tar into aromatics, especially PAH. Soot appears to be a major product from homogeneous secondary tar reactions.