Hydrodynamic gas-solid model of cupric chloride particles reacting with superheated steam for thermochemical hydrogen production

This paper examines the transport phenomena of a non-catalytic reaction of cupric chloride particles with superheated steam in a fluidized bed, as part of a copper-chlorine (Cu-Cl) thermochemical cycle for nuclear-based hydrogen production. As both cupric chloride and steam participate in the chemical reaction, it is necessary to develop a new model that predicts the conversion of cupric chloride particles, as well as steam. This incorporates features of a uniform reaction model (Volumetric Model; VM) and a Shrinking Core Model (SCM). Due to little or no experimental data available for the hydrodynamics and chemistry of the reaction, the above two models are considered as limiting cases. Separate numerical solution procedures are developed to monitor the effects of various parameters on the conversion of CuCl₂ particles and steam. Also, the new solution algorithms are used to predict outputs for a typical bench-scale reactor and operating conditions. From the numerical results, under the assumption of VM or SCM, the conversion of steam decreases with superficial velocity, whereas the conversion of solid particles increases. Also, a higher bed inventory leads to higher conversion of both reactants. SCM predicts higher values for the reactant conversions, compared to VM. The new solution procedures may be utilized for parametric studies that observe the effects of different process parameters on the fluidized bed performance.     

Control of fluidized bed coating particles using Gaussian spectral pressure distribution

Fluidization has been used extensively in many industrial processes in chemical, food and pharmaceutical branches. However, the operational conditions of these processes frequently lead to the defluidization phenomenon or to the total collapse of the particles in the bed. The maintenance of stable conditions in the fluidization regime during fluidized bed coating processes is very important, because the moisture content excess can cause the defluidization of the bed. The objective of this work was to apply a new methodology, known as Gaussian spectral pressure distribution, to monitor and control the defluidization phenomenon in a fluidized bed coating process using microcrystalline cellulose as fluidizing particles. The work was performed in two stages: 1) monitoring of the fluidization regimes during the development of the coating process without control and 2) control of the airflow rate and of the coating suspension flow rate using PI controllers. The experiments were carried out varying solid particle mass, coating suspension flow rate and excess air velocity in relation to the minimum fluidization velocity working with a temperature of 70 °C. The Gaussian mean frequency evolution showed the fluidization regime transitions and it allowed to define a band of stable regime (6.0 Hz to 7.0 Hz), which was used as a set-point range of the controllers to manipulate the signal of command for frequency converter and for the peristaltic pump. The application of Åström and Hägglund [29] method allowed obtaining the PI controller parameters for the converter and the reaction curve method provided an initial guess of the PI controller parameters for the pump. The experiments of microcrystalline cellulose coating in closed-loop showed that the use of a control system allowed obtaining better fluid-dynamic conditions of the bed in relation to the process without control.     

High-temperature de fluidization

Operation of fluidized beds at high temperatures is limited by the tendency of the bed particles to agglomerate, causing defluidization. This operating limit is important in several processes, including coal conversion, iron ore reduction, and cement manufacture.At lower temperatures, the bed remains fluidized at velocities above the normal minimum fluidization velocity. Once the bed is operating above an ‘Initial Sintering Temperature’, the fluid velocity must be well above the normal minimum fluidization velocity in order to prevent defluidization. The defluidization velocity increases with increasing operating temperature. The ‘Initial Sintering Temperature’ can be estimated using a dilatometer to measure thermal expansion and contraction of a loosly packed sample of the bed particles.     

Cold flow experimental study and computer simulations of a compact spouted bed reactor

Spouted beds are a very interesting class of gas–solid contactors that possess excellent heat transfer and mixing characteristics, while they are particularly suited to process coarse particles. Proper design of such beds requires the prediction of various hydrodynamic characteristics, such as the minimum spouting velocity and maximum spoutable height. Contrary to their typical initial applications, spouted beds have been finding recently more frequent use on the one hand at endothermic processes and on the other hand using much finer particle sizes. In the current work, the hydrodynamic characteristics of a laboratory scale spouted bed of 0.05 m diameter have been investigated via cold flow studies using olivine particles of 3.55–5.00 × 10⁻⁴ m size. Hydrodynamic parameters have been measured at this compact geometry and fine particle size and were compared with common literature correlations. An empirical correlation was derived to predict the fountain height for the studied fine particle spouted bed. Computer simulations have been further used to investigate the heat transfer characteristics of the bed under endothermic reactive conditions, using methane reforming as a case study. Given sufficient external heat supply, a spouted bed operating at a well-mixed regime can efficiently drive even highly endothermic reactions.     

A novel reverse flow reactor coupling endothermic and exothermic reactions: Part II: Sequential reactor configuration for reversible endothermic reactions

The new reactor concept for highly endothermic reactions at elevated temperatures with possible rapid catalyst deactivation based on the indirect coupling of endothermic and exothermic reactions in reverse flow, developed for irreversible reactions in Part I, has been extended to reversible endothermic reactions for the sequential reactor configuration. In the sequential reactor configuration, the endothermic and exothermic reactants are fed discontinuously and sequentially to the same catalyst bed, which acts as an energy repository delivering energy during the endothermic reaction phase and storing energy during the consecutive exothermic reaction phase. The periodic flow reversals to incorporate recuperative heat exchange result in low temperatures at both reactor ends, while high temperatures prevail in the centre of the reactor. For reversible endothermic reactions, these low exit temperatures can shift the equilibrium back towards the reactants side, causing ‘back-conversion’ at the reactor outlet.The extent of back-conversion is investigated for the propane dehydrogenation/methane combustion reaction system, considering a worst case scenario for the kinetics by assuming that the propylene hydrogenation reaction rate at low temperatures is only limited by mass transfer. It is shown for this reaction system that full equilibrium conversion of the endothermic reactants cannot be combined with recuperative heat exchange, if the reactor is filled entirely with active catalyst. Inactive sections installed at the reactor ends can reduce this back-conversion, but cannot completely prevent it. Furthermore, undesired high temperature peaks can be formed at the transition point between the inactive and active sections, exceeding the maximum allowable temperature (at least for the relatively fast combustion reactions).A new solution is introduced to achieve both full equilibrium conversion and recuperative heat exchange while simultaneously avoiding too high temperatures, even for the worst case scenario of very fast propylene hydrogenation and fuel combustion reaction rates. The proposed solution utilises the movement of the temperature fronts in the sequential reactor configuration and employs less active sections installed at either end of the active catalyst bed and completely inactive sections at the reactor ends, whereas propane combustion is used for energy supply. Finally, it is shown that the plateau temperature can be effectively controlled by simultaneous combustion of propane and methane during the exothermic reaction phase.     

Model‐based optimization of hydrogen generation by methane steam reforming in autothermal packed‐bed membrane reformer

An autothermal membrane reformer comprising two separated compartments, a methane oxidation catalytic bed and a methane steam reforming bed, which hosts hydrogen separation membranes, is optimized for hydrogen production by steam reforming of methane to power a polymer electrolyte membrane fuel cell (PEMFC) stack. Capitalizing on recent experimental demonstrations of hydrogen production in such a reactor, we develop here an appropriate model, validate it with experimental data and then use it for the hydrogen generation optimization in terms of the reformer efficiency and power output. The optimized reformer, with adequate hydrogen separation area, optimized exothermic‐to‐endothermic feed ratio and reduced heat losses, is shown to be capable to fuel kW‐range PEMFC stacks, with a methane‐to‐hydrogen conversion efficiency of up to 0.8. This is expected to provide an overall methane‐to‐electric power efficiency of a combined reformer‐fuel cell unit of ～0.5. Recycling of steam reforming effluent to the oxidation bed for combustion of unreacted and unseparated compounds is expected to provide an additional efficiency gain. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Effects of microreactor wall heat conduction on the reforming process of methane

In this paper, the effect of wall conduction of an autothermal tubular methane microreformer is investigated numerically. It is found that the axial wall conduction can strongly influence the performance of the microreactor and should not be neglected without a careful a priori investigation of its impact. By increasing the wall thermal conductivity, the maximum wall surface temperature is decreased. Due to the complex exothermic–endothermic nature of the chemistry of reforming, the axial variation of the wall temperature is not monotonic. Methane conversion and hydrogen yield are strongly dependent on the wall inner surface temperature, hence the heat conduction through the channel wall. The equivalence ratio and the wall thickness also significantly affect the reforming effectiveness and must be carefully considered in reactor optimization. Furthermore, it is found that exothermic oxidation reaction mechanisms, especially partial oxidation, are responsible for syngas (hydrogen and carbon monoxide) production near the inlet. Farther downstream, in the oxygen deficient region, endothermic steam reforming is the main hydrogen producing mechanism. By increasing the thermal conductivity, steam reforming becomes stronger and partial oxidation becomes weaker. For all investigated inlet conditions, the highest hydrogen yield is obtained for no or very low conductive walls.     

ONBOARD FUEL CONVERSION FOR HYDROGEN-FUEL-CELL-DRIVEN VEHICLES

Increasingly stringent legislation controls emissions from internal combustion engines to the point where alternative power sources for vehicles are necessary. The hydrogen fuel cell is one promising option, but the nature of the gas is such that the conversion of other fuels to hydrogen on board the vehicle is necessary.

The conversion of methanol, methane, propane, and octane to hydrogen is reviewed. A combination of oxidation and steam reforming (indirect partial oxidation) or direct partial oxidation are the most promising processes. Indirect partial oxidation involves combustion of part of the fuel to produce sufficient heat to drive the endothermic steam reforming reaction. Direct partial oxidation is favored only at high temperatures and short residence times but is highly selective. However, indirect partial oxidation is shown to be the preferred process for all fuels.

The product gases can be taken through a water–gas shift reactor, but still retain ～2% carbon monoxide, which poisons fuel-cell catalysts. Selective oxidation is the preferred route to removal of residual carbon monoxide. Low-temperature oxidation in the absence and presence of an excess of hydrogen is reviewed. Au-based catalysts show much promise, but precious metal catalysts such as Pt/zeolite have some advantages.     

A fluidized bed membrane reactor for the steam reforming of methane

In the present investigation a realistic two-phase model accounting for the change in the total number of moles accompanying the reaction is utilized to explore a novel reactor configuration suggested for the methane steam reforming process. The suggested design is basically a fluidized bed reactor equipped with a bundle of membrane tubes. These tubes remove the main product, hydrogen, from the reacting gas mixture and drive the reaction beyond its thermodynamic equilibrium. The proposed novel design is also equipped with sodium heat pipes which act as a thermal flux transformer to provide the large amount of heat needed by the endothermic reaction through a relatively small heat transfer surface, assuring better reactor compactness. Two options for fluid routing through the membrane tubes are proposed; each is suitable for a certain industrial application. The performance of this novel configuration is compared with that of an industrial fixed bed steam reformer and the comparison shows the potential advantages of the suggested configuration.     

4-氯-2-三氟甲基苯胺的合成

以邻三氟甲基苯胺为起始原料,二水氯化铜为催化剂,盐酸-双氧水为氯化剂,合成4-氯-2-三氟甲基苯胺。研究了催化剂、盐酸用量和温度对反应的影响。通过设计一组正交实验,得到了较优反应条件。当原料、催化剂、盐酸的摩尔比为1：1：10,滴加双氧水的温度为0℃时,实验结果最好,转化率达95％,目标产物的选择性80％以上。     

Modeling a low pressure steam-oxygen fluidized bed coal gasifying reactor

A comprehensive model accounting for the jetting region and homogeneous dilute phase reactions is developed for the adiabatic and continuous gasification of coal particles in a fluidized bed. The division of flows in the bed is determined by means of a modified two-phase theory which considers inlet gas jets, bubbles, free of particles, which develop at the top of the jets and grow in size as they rise, and an emulsion phase consisting of particles and the surrounding interstitial gas. The model describes the gasification of coal particles by pyrolytic devolatilization and three heterogeneous chemical reactions: oxidation by oxygen and steam, and reduction of carbon dioxide. Carbon monoxide and hydrogen produced by the heterogeneous reactions can be oxidized to carbon dioxide and steam by incoming oxygen within the dilute phase jets and bubbles. Furthermore, the water-gas shift reaction can occur in the dilute phase and interstitial gas. Simulations both with and without homogeneous reactions occurring in the jets and bubbles indicate that dilute phase homogeneous reactions have considerable influence on carbon conversion, bed temperature, and product gas composition. It has also been found that the jetting-emulsion mass and beat interchange has a substantial effect on overall bed performance and the temperature of the bed close to the inlet gas distributor. Results indicate that water-gas shift equilibrium is established rapidly and significant quantities of hydrogen and carbon monoxide and a nonuniform steam concentration are present within the combustion zone.     

A novel induction heating fluidized bed reactor: Its design and applications in high temperature screening tests with solid feedstocks and prediction of defluidization state

A novel mini induction heating fluidized bed reactor (IHFBR) is introduced which was developed to carry out screening tests of high temperature reactions up to 1500°C particularly for solid feedstocks. Despite conventional mini reactors, this reactor mimics real scenario of solid feeding in industrial reactors: cold feedstock is injected within 1 s from a lift tube, then particles reach reaction temperature in less than 5 s in a reaction zone. The lift tube (9.5 cm diameter) is also the gas distributor of the fluidized bed (2.5 cm diameter) so that the bed is completely fluidized with uniform gas distribution. Beside facilities to perform tests in a fluidized bed, another important feature of this reactor is prediction of the defluidization state in the bed. Not only reproducible data are generated, but also many tests can be conveniently carried out, that is, one test per hour. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1507–1523, 2015     

串行流化床煤气化试验

针对串行流化床煤气化技术特点,以水蒸气为气化剂,在串行流化床试验装置上进行煤气化特性的试验研究,考察了气化反应器温度、蒸汽煤比对煤气组成、热值、冷煤气效率和碳转化率的影响。结果表明,燃烧反应器内燃烧烟气不会串混至气化反应器,该煤气化技术能够稳定连续地从气化反应器获得不含N₂的高品质合成气。随着气化反应器温度的升高、蒸汽煤比的增加,煤气热值和冷煤气效率均会提高,但对碳转化率影响有所不同。在试验阶段获得的最高煤气热值为6.9 MJ•m^-3,冷煤气效率为68％,碳转化率为92％。     

Agglomeration of coal ash in fluidized beds

The defluidization behaviour of ash derived from Indian coal by combustion in a fluidized bed has been studied. Sintering temperatures for ash in several ranges of particle size were measured with a dilatometer. In agreement with the earlier work on other coals it was found that above the sintering temperature pairs of complementary, limiting values of fluidization velocity and bed temperatures exist which mark the onset of defluidization when the ash particles are heated in a fluidized bed. A linear relation was observed between bad temperature and limiting defluidization velocity. The constants in the corresponding equations were calculated for two size ranges of particles.     

A novel slurry bubble column membrane reactor concept for Fischer–Tropsch synthesis in GTL technology

Fischer–Tropsch synthesis (FTS) plays an important role in the production of ultra-clean transportation fuels, chemicals, and other hydrocarbon products. In this work, a novel combination of fixed-bed and slurry bubble column membrane reactor for Fischer–Tropsch synthesis has been proposed. In the first catalyst bed, the synthesis gas is partially converted to hydrocarbons in a water-cooled reactor which is fixed bed. In the second bed which is a membrane assisted slurry bubble column reactor, the heat of reaction is used to preheat the feed synthesis gas to the first reactor. Due to the decrease of H₂/CO to values far from optimum reactants ratio, the membrane concept is suggested to control hydrogen addition. A one-dimensional packed-bed model has been used for modeling of fixed-bed reactor. Also a one-dimensional model with plug flow pattern for gas phase and an axial dispersion pattern for liquid-solid suspension have been developed for modeling of slurry bubble column reactor. Proficiency of a membrane FTS reactor (MR) and a conventional FTS reactor (CR) at identical process conditions has been used as a basis for comparison in terms of temperature, gasoline yield, H₂ and CO conversion as well as selectivity. Results show a favorable temperature profile along the proposed concept, an enhancement in the gasoline yield and, thus a main decrease in undesirable product formation. The results suggest that utilizing this type of reactor could be feasible and beneficial. Experimental proof of concept is needed to establish the validity and safe operation of the proposed reactor.     

Hydrogen Production by Sorption‐Enhanced Steam Glycerol Reforming: Sorption Kinetics and Reactor Simulation

Sorption‐enhanced glycerol reforming, an integrated process involving glycerol catalytic steam reforming and in situ CO₂ removal, offers a promising alternative for single‐stage hydrogen production with high purity, reducing the abundant glycerol by‐product streams. This work investigates this process in a fixed‐bed reactor, via a two‐scale, nonisothermal, unsteady‐state model, highlighting the effect of key operating parameters on the process performance. CO₂ adsorption kinetics was investigated experimentally and described by a mathematical reaction‐rate model. The integrated process presents an opportunity to improve the economics of green hydrogen production via an enhanced thermal efficiency process, the exothermic CO₂ adsorption providing the heat to endothermic steam glycerol reforming, while reducing the capital cost by removing the processing steps required for subsequently CO₂ separation. The operational time of producing high‐purity hydrogen can be enhanced by increasing the adsorbent/catalyst volume ratio, by adding steam to the reaction system and by increasing the inlet reactor temperature. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2105–2118, 2013     

松木屑颗粒热解过程中的热/质传递规律

为探索在固定床反应器中有机固废颗粒热解过程中的热量、质量传递机理,本研究从颗粒尺度上对有机固废松木屑颗粒热解过程建模分析,模型中考虑了焦油的二次裂解反应及挥发分在颗粒孔隙中的质量、动量传递过程,并采用达西定律模拟了挥发分在颗粒孔隙内的流动现象,对颗粒热解过程的吸热反应以及挥发分逸出时的对流换热对颗粒温度的影响进行考察。基于两步反应动力学模型,探讨了不同颗粒尺寸、热解温度对有机固废松木屑颗粒热解过程的影响。结果表明,热解吸热反应和挥发分的对流换热阻碍了热量向颗粒中心的传递,延长了颗粒达到均温的时间;松木屑颗粒热解时,颗粒内会存在明显的温度梯度,在颗粒表面主要受化学反应动力学限制,在颗粒内部则主要受热量传递过程限制。此外,热解温度越低,粒径越大,颗粒内部的传热阻力越大。松木屑颗粒完全热解所需时间会随着颗粒粒径的增大而增加,但当颗粒粒径在10mm以上时,随着颗粒粒径的增大,颗粒完全热解所需时间的增量要大于10mm以下颗粒。     

ONBOARD FUEL CONVERSION FOR HYDROGEN-FUEL-CELL-DRIVEN VEHICLES

Increasingly stringent legislation controls emissions from internal combustion engines to the point where alternative power sources for vehicles are necessary. The hydrogen fuel cell is one promising option, but the nature of the gas is such that the conversion of other fuels to hydrogen on board the vehicle is necessary.

The conversion of methanol, methane, propane, and octane to hydrogen is reviewed. A combination of oxidation and steam reforming (indirect partial oxidation) or direct partial oxidation are the most promising processes. Indirect partial oxidation involves combustion of part of the fuel to produce sufficient heat to drive the endothermic steam reforming reaction. Direct partial oxidation is favored only at high temperatures and short residence times but is highly selective. However, indirect partial oxidation is shown to be the preferred process for all fuels.

The product gases can be taken through a water-gas shift reactor, but still retain ∼2% carbon monoxide, which poisons fuel-cell catalysts. Selective oxidation is the preferred route to removal of residual carbon monoxide. Low-temperature oxidation in the absence and presence of an excess of hydrogen is reviewed. Au-based catalysts show much promise, but precious metal catalysts such as Pt/zeolite have some advantages.     

Experimental study on CO2 capture conditions of a fluidized bed limestone decomposition reactor

In this study, the decomposition conditions of limestone particles (0.25-0.50 mm) for CO₂ capture in a steam dilution atmosphere (20-100% steam in CO₂) were investigated by using a continuously operating fluidized bed reactor. The results show that the decomposition conversion of limestone increased with the steam dilution percentage in the CO₂ supply gas. At a bed temperature of 920 °C, the conversions were 72% without steam dilution and 98% with 60% steam dilution. The conversion was 99% with 100% steam dilution at 850 °C of the bed temperature. Steam dilution can decrease not only the decomposition temperature of limestone, but also the residence time required for nearly complete decomposition of CaCO₃. The hydration and carbonation reactivities of the CaO produced were also tested and the results show that both the reactivities increased with the steam dilution percentage for decomposing limestone.     

Application of Danckwerts-type boundary conditions to the modeling of the thermal behavior of metal hydride reactors

The paper presents a model-based investigation of a metal hydride reactor applied as a solid state hydrogen storage device. The elements of a metal hydride reactor are hydrogen supply duct, internal hydrogen distribution, hydride bed, reactor shell and the flow domain of the heat transfer fluid. Internal hydrogen distribution and hydride bed are porous media. Therefore, hydrogen flows through non-porous and porous regions during its reversible exothermic absorption and endothermic desorption, respectively. The interface between porous and non-porous regions is a discontinuity with respect to energy transport mechanisms. Hence, Danckwerts-type boundary conditions for the energy balance equation are introduced. Application of the first and second law of thermodynamics to the interface reveals that temperature jumps may occur at the hydrogen inlet but are not allowed at the hydrogen outlet. Exemplarily the loading behavior of a metal hydride storage tank based on sodium alanate is analyzed. It is demonstrated and experimentally validated that only Danckwerts-type boundary conditions predict the important cooling effect of the inlet hydrogen on the exothermic absorption process correctly.