A packed‐bed solar reactor for the carbothermal zinc production – dynamic modelling and experimental validation

Integration of concentrated solar energy into the pyrometallurgical Zn production process as clean source of high‐temperature process heat could significantly reduce fossil fuels consumption and its concomitant CO₂ emissions. The solar‐driven carbothermal reduction of ZnO is investigated using a 10‐kW_th solar reactor featuring two cavities, the upper one serving as the solar absorber and the lower one containing a packed‐bed of ZnO and beech charcoal as the biogenic reducing agent. Experimentation in a high‐flux solar simulator is carried out under radiative fluxes of 2300–2890 suns, yielding a peak solar‐to‐chemical energy conversion efficiency of 18.4%. The reactor performance under variable operating conditions is analyzed via a dynamic numerical model coupling heat transfer with chemical kinetics. The model is validated by comparison to the experimental data obtained with the 10‐kW_th packed‐bed solar reactor and further applied to predict the effect of incorporating semi‐continuous feeding of reactants on the process efficiency. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4586–4594, 2016     

Experimental investigation of a packed-bed solar reactor for the steam-gasification of carbonaceous feedstocks

Steam-gasification of coal, biomass, and carbonaceous waste feedstocks for syngas production is performed using concentrated solar energy as the source of high-temperature process heat. The solar reactor consists of two cavities separated by a SiC-coated graphite plate, with the upper one serving as the radiative absorber and the lower one containing the reacting packed bed that shrinks as the reaction progresses. The carbonaceous feedstocks tested were industrial and sewage sludges, scrap tire powder, fluff, South African coal, and beech charcoal, and are characterized by having a wide range of volatile, ash, and fixed carbon contents, elemental compositions, and physical properties. A 5 kW solar reactor prototype, subjected to radiative flux concentrations up to 2953 suns and operated at temperatures up to 1490 K, yielded high-quality syngas of typical molar ratios H₂/CO = 1.5 and CO₂/CO = 0.2, and with a calorific content up to 30% upgraded over that of the input feedstock. Solar-to-chemical energy conversion efficiencies varied between 17.3% and 29%. Pyrolysis was evident through the evolution of higher gaseous hydrocarbons and liquid tars during heating of the packed bed. The engineering design, fabrication, and testing of the solar reactor are described.     

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     

CO2 reduction with Zn particles in a packed‐bed reactor

A two‐step solar thermochemical cycle for splitting CO₂ with Zn/ZnO redox reactions is considered, consisting of: (1) the endothermic dissociation of ZnO with concentrated solar radiation as the heat source and (2) the non‐solar, exothermic, reduction of CO₂ to CO by oxidizing Zn to ZnO; the latter is recycled to the first step. The second step of the cycle is investigated using a packed‐bed reactor where micron‐sized Zn particles were immobilized in mixtures with submicron‐sized ZnO particles. Experimental runs were performed for Zn mass fractions in the range 67–100 wt % and CO₂ concentration in the range 25–100%, yielding Zn‐to‐ZnO conversions up to 71% because of sintering prevention, as corroborated by SEM analysis. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Packed‐bed reactor for short time gas phase olefin polymerization: Heat transfer study and reactor optimization

A specially conceived packed‐bed stopped flow minireactor (3 mL) suitable for short gas phase catalytic reactions has been used to study the start‐up of ethylene homopolymerization with a supported metallocene catalyst. Focus has been put on the heat transfer characteristics of the supported catalysts and on understanding the relationship between the initial rate and the relative gas/particle velocities and the influence of particle parameters in the packed bed. We performed a comprehensive study on the influence of various physical parameters on the heat transfer regime at start up conditions. The catalyst activity as well as the polymer morphology is shown to be dependent on heat transfer regime. The knowledge thus obtained is applicable to industrial problems like catalyst injection in fluidized beds and helps preventing experimental artifacts due to overheating in following studies. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Dynamics and control of solar thermochemical reactors

A general dynamic model for solar-driven thermochemical processes is formulated based on unsteady mass and energy conservation equations coupled to the reaction kinetics. It is applied to two pertinent high-temperature thermochemical reactors for fuel production that make use of concentrated solar energy as the source of process heat, namely: an indirectly irradiated batch-operated packed bed reactor for the carbothermic reduction of zinc oxide, and a directly irradiated continuously operated particle flow reactor for the steam-gasification of petcoke. Model parameter identification and validation is accomplished by comparing numerically simulated and experimentally measured temperatures and outlet product concentrations. A linear feedback controller was implemented using the LQG/LTR design method. Simulations of the controlled reactor system with real solar irradiation data indicates improved quality and steadiness of product composition throughout transient solar input phases and superior solar-to-chemical energy conversion efficiency.     

Analysis of solar‐driven gasification of biochar trickling through an interconnected porous structure

The efficient transfer of high‐temperature solar heat to the reaction site is crucial for the yield and selectivity of the solar‐driven gasification of biomass. The performance of a gas‐solid trickle‐bed reactor constructed from a high thermal conductivity porous ceramic packing has been investigated. Beech char particles were used as the model feedstock. A two‐dimensional finite‐volume model coupling chemical reaction with conduction, convection, and radiation of heat within the packing was developed and tested against measured temperatures and gasification rates. The sensitivity of the gasification rate and reactor temperatures to variations of the packing's pore diameter, porosity, thermal conductivity, and particle loading was numerically studied. A numerical comparison with a moving bed projected a more uniform temperature distribution and higher gasification rates due to the increased heat transfer via combined radiation and conduction through the trickle bed. © 2014 American Institute of Chemical Engineers AIChE J, 61: 867–879, 2015     

A Novel Fluidized‐Bed Membrane Dual‐Type Reactor Concept for Methanol Synthesis

A novel fluidized‐bed membrane dual‐type methanol reactor (FBMDMR) concept is proposed in this paper. In this proposed reactor, the cold feed synthesis gas is fed to the tubes of the gas‐cooled reactor and flows in counter‐current mode with a reacting gas mixture in the shell side of the reactor, which is a novel membrane‐assisted fluidized bed. In this way, the synthesis gas is heated by heat of reaction which is produced in the reaction side. Hydrogen can penetrate from the feed synthesis gas side into the reaction side as a result of a hydrogen partial pressure difference between both sides. The outlet synthesis gas from this reactor is fed to tubes of the water‐cooled packed bed reactor and the chemical reaction is initiated by the catalyst. The partially converted gas leaving this reactor is directed into the shell of the gas‐cooled reactor and the reactions are completed in this fluidized‐bed side. This reactor configuration solves some drawbacks observed from the new conventional dual‐type methanol reactor, such as pressure drop, internal mass transfer limitations, radial gradient of concentration, and temperature in the gas‐cooled reactor. The two‐phase theory of fluidization is used to model and simulate the proposed reactor. An industrial dual‐type methanol reactor (IDMR) and a fluidized‐bed dual‐type methanol reactor (FBDMR) are used as a basis for comparison. This comparison shows enhancement in the yield of methanol production in the fluidized‐bed membrane dual‐type methanol reactor (FBMDMR).     

Structured Porous Millireactors for Liquid‐Liquid Chemical Reactions

Milli‐scale reactors with an integrated microstructure offer a promising scale‐up approach for conventional microreactors. This study applies 3D‐printed structured porous millireactors to industrially relevant liquid‐liquid reactions. The underlying transport mechanisms are identified by quantifying interfacial heat and mass transfer. The structured reactors perform limited in Taylor flow compared to a packed‐bed reactor due to limited interfacial mass transfer. However, in stratified flow, their productivity increases significantly at a fraction of the pressure drop of a packed bed.     

Pilot Scale Continuous Microwave Dry‐Media Reactor – Part 1: Design and Modeling

This work presents a new pilot plant continuous microwave dry‐media reactor (CMDR) for industrial chemical applications. The CMDR consists of a 6 kW conveyor microwave oven with a subsequent hot air holding section. This microwave reactor has been designed for dry media or solvent‐free reactions and can treat through‐put in the range of 10–100 kg/h. The microwave heating behavior on the small scale is analyzed and the results are used to estimate the electromagnetic field requirements on the large scale. The temperature and the electric field distribution in the reactor are modeled and experimentally validated. In the second part of this study, a “waxy” esterification reaction was investigated with the CMDR. The reaction time needed for 95% yield was reduced by a factor of 20–30 compared to conventional industrial reactors. This was due to the more homogeneous heat transfer of microwaves, which allows a higher bulk temperature to be reached.     

Syngas production from H2O and CO2 over Zn particles in a packed‐bed reactor

The solar thermochemical production of H₂ and CO (syngas) from H₂O and CO₂ is examined via a two‐step cycle based on Zn/ZnO redox reactions. The first, endothermic step is the thermolysis of the ZnO driven by concentrated solar energy. The second, nonsolar step is the exothermic reaction of Zn with a mixture of H₂O and CO₂ yielding syngas and ZnO; the latter is recycled to the first step. A series of experimental runs of the second step was carried out in a packed‐bed reactor where ZnO particles provided an effective inert support for preventing sintering and enabling simple and complete recycling to the first, solar step. Experimentation was performed for Zn mass fractions in the range of 33–67 wt % Zn‐ZnO, and inlet gas concentrations in the range 0–75% H₂O–CO₂, yielding molar Zn‐to‐ZnO conversions up to 91%. A 25 wt % Zn‐ZnO sample mixture produced from the solar thermolysis of ZnO was tested in the same reactor setup and exhibited high reactivity and conversions up to 96%. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

The aromatic enhancement in the axial‐flow spherical packed‐bed membrane naphtha reformers in the presence of catalyst deactivation

Because of some disadvantages of conventional tubular reactors (CTRs), the concept of spherical membrane reactors is proposed as an alternative. In this study, it is suggested to apply hydrogen perm‐selective membrane in the axial‐flow spherical packed‐bed naphtha reformers. The axial flow spherical packed‐bed membrane reactor (AF‐SPBMR) consists of two concentric spheres. The inner sphere is supposed to be a composite wall coated by a thin Pd‐Ag membrane layer. Set of coupled partial differential equations are developed for the AF‐SPBMR model considering the catalyst deactivation, which are solved by using orthogonal collocation method. Differential evolution optimization technique identifies some decision variables which can manipulate the input parameters to obtain the desired results. In addition to lower pressure drop, the enhancement of aromatics yield by the membrane layer in AF‐SPBMR adds additional superiority to the spherical reactor performance in comparison with CTR. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Optimal operation of a membrane reactor network

In this contribution, the operation of a membrane reactor network (MRN) for the oxidative coupling of methane is optimized. Therefore, three reactors, a fixed bed reactor (FBR) and two packed bed‐membrane reactors, are modeled. For the (CPBMR), a two‐dimensional (2‐D) model is presented. This model incorporates radial diffusion and thermal conduction. In addition, two 10 cm long cooling segments for the CPBMR are implemented based on the idea of a fixed cooling temperature positioned outside the reactor shell. The model is discretized using a newly developed 2‐D orthogonal collocation on finite elements with a combination of Hermite for the radial and Lagrangian polynomials for the axial coordinate. Membrane thickness, feed compositions, temperatures at the inlet and for the cooling, diameters, and the amount of inert packing in the reactors are considered as decision variables. The optimization results in C₂ yields of up to 40% with a selectivity in C₂ products of more than 60%. The MRN consisting of an additional packed‐bed membrane reactor with an alternative feeding policy and a FBR shows a lower yield than the individual CPBMR. © 2013 American Institute of Chemical Engineers AIChE J, 60: 170–180, 2014     

Heat transfer model of a solar receiver-reactor for the thermal dissociation of ZnO—Experimental validation at 10 kW and scale-up to 1 MW

A transient heat transfer model is developed for analyzing the thermal performance of a thermochemical reactor for the solar-driven dissociation of ZnO in the 1600–2136 K range. The reactor consists of a rotating cavity-receiver lined with ZnO particles that are directly exposed to concentrated solar radiation. The model couples radiation, convection, and conduction heat transfer to the reaction kinetics for a shrinking domain and simulates a transient ablation regime with semi-batch feed cycles of ZnO particles. Validation is accomplished in terms of the numerically calculated and experimentally measured temperature profiles and reaction extents for a 10 kW reactor prototype tested in a high-flux solar simulator and subjected to peak solar concentration ratios exceeding 5000 suns. Scaling-up the reactor technology to 1 MW solar thermal power input has the potential of reaching a solar-to-chemical energy conversion efficiency of 56%.     

Fixed‐Bed Heat Storage – Mathematical Modeling Approaches

While renewable heat makes up only 13 % of overall German heat consumption, the share of renewable electricity produced from wind, solar, water, and geothermal power already reached 36 % of overall electricity consumption in 2017. One measure to support the integration of renewable heat in the German energy system is the use of heat storage systems. Although water‐based heat storage systems for temperatures up to 100 °C are state of the art, systems for temperatures up to several hundred degrees Celsius are still under investigation or in the demonstration phase. Therefore, this work focuses on the development of a simulation model for analyzing and engineering fixed‐bed thermal storage systems that are filled with an inert bulk material such as stone fragments.     

Performance of a ZVI‐UASB reactor for azo dye wastewater treatment

BACKGROUND: Zero valent iron (ZVI) is expected to be helpful for creating an enhanced anaerobic environment that might improve the performance of the anaerobic process. Based on this idea, a ZVI packed upflow anaerobic sludge blanket reactor (ZVI‐UASB) was developed to enhance azo dye wastewater treatment. RESULTS: The ZVI‐UASB reactor was less influenced by a decrease in the operational temperature from 35 °C to 25 °C than a reference UASB reactor that did not contain ZVI. In addition, chemical oxygen demand (COD) and color removal efficiencies of the ZVI‐UASB reactor at an HRT of 12 h exceeded those of the reference reactor at an HRT of 24 h. The hydraulic circulation in the ZVI bed enhanced the function of ZVI so that it improved the COD and color removal efficiencies. Moreover, fluorescence in situ hybridization experiments revealed that the abundance of Archaea in the sludge of the ZVI bed was significantly higher than that at the reactor bottom, which made the reactor capable of greater COD removal under low temperature and short HRT conditions. CONCLUSION: This ZVI‐UASB reactor could adapt well to changes in the operational conditions during wastewater treatment. Copyright © 2010 Society of Chemical Industry     

Fixed‐Bed Multi‐Tubular Reactors for Oxidative Dehydrogenation in Ethylene Process

An industrial‐scale reactor for ethylene production was modeled using the oxidative dehydrogenation of ethane (ODHE) in a multi‐tubular reactor system, examining a variety of parameters affecting reactor performance. The model showed that a double‐bed multi‐tubular reactor with intermediate air injection scheme was superior to a single‐bed design, due to the increased ethylene selectivity while operating under lower oxygen partial pressures. The optimized reactor length for 100 % oxygen conversion was theoretically determined for both reactor designs. The use of a distributed oxygen feed with a limited number of injection points indicated a significant improvement on the reactor performance in terms of ethane conversion and ethylene selectivity. This concept also overcame the reactor runaway temperature problem and enabled operations over a wider range of conditions to obtain enhanced ethylene production.     

Dynamic Charging Performance of a Solar Latent Heat Storage Unit for Efficient Energy Utilization

The dynamic charging performance of a solar heat storage system involving a packed bed containing spherical capsules is studied. The dynamic charging process of the solar heat storage system is simulated according to the energy balance equations. Paraffin is used as the phase change material (PCM) and water is used as the heat transfer fluid (HTF). The temperatures of the PCM and HTF, melting fraction and solar heat storage capacity are illustrated and analyzed. The influences of inlet temperature, initial temperature and flow rate of HTF, and the porosity of the packed bed on the charging time and heat storage capacity during the heat storage process are also discussed.     

Modeling of a multizone gas‐phase polyethylene reactor with a cluster‐based approach

A circulating fluidized reactor of polyethylene was modeled with the proper hydrodynamics for a riser and downer and combined with a kinetic model based on the moment equations. The hydrodynamic model was able to predict the profiles of the following parameters through the riser and downer: cluster velocity, bed porosity, concentration of potential active sites, active sites, gas‐phase components, molecular weights, and reactor temperature. It was shown that one could control the monomer consumption and molecular weight, which are crucial in the reactor behavior and production properties, respectively, by setting different operating hydrodynamic conditions, such as the gas velocity in the riser and the solid circulation rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Heterogeneous Reactor Modeling of an Industrial Multitubular Packed‐Bed Ethylene Oxide Reactor

The one‐dimensional heterogeneous model of an industrial multitubular packed‐bed ethylene oxide (EO) reactor was developed using the equation‐oriented platform Aspen Custom Modeler. Reactor operation was optimized in terms of maximized EO production and selectivity and enhanced safety related to the presence of oxygen in the EO reactor. Good agreement was found between the model results during validation against the available information under identical operating conditions. The model predicts the behavior of the EO reaction and demonstrates the extent of catalyst utilization with product distribution, product yield, by‐product formation, temperature and concentration profiles, over time and along the length of the reactor or catalyst bed. The model sensitivity studies compute the optimum feed flow, oxygen concentration, feed pressure, etc. and suggest the best operational philosophy.