Recent trends in the development of reactor systems for hydrogen production via methanol steam reforming

Hydrogen is currently receiving significant attention as an alternative energy resource, and among the various methods for producing hydrogen, methanol steam reforming (MSR) has attracted great attention because of its economy and practicality. Because the MSR reaction is inherently activated over catalytic materials, studies have focused on the development of noble metal-based catalysts and the improvement of existing catalysts with respect to performance and stability. However, less attention has been paid to the modification and development of innovative MSR reactors to improve their performance and efficiency. Therefore, in this review paper, we summarize the trends in the development of MSR reactor systems, including microreactors and membrane reactors, as well as the various structured catalyst materials appropriate for application in complex reactors. In addition, other engineering approaches to achieve highly efficient MSR reactors for the production of hydrogen are discussed.     

Analysis of operating limits and combustion state regulation for low-calorific value gases in industrial burners

The effective and efficient utilization of low-calorific value (LCV) gases has gained increasing attention in scientific research and industrial fields. In this study, the combustion characteristics of three LCV gases in practical devices are analyzed by using a nonadiabatic perfectly stirred reactor model. The complete steady-state solution in the temperature-residence time parameter space is obtained with arc-length continuation. The stable operation region is quantified by the eigenvalue analysis. The transition of solution curves is quantified with heat loss coefficient. Five key system parameters are systematically investigated on their effects on stability limits. With the combustion performance being quantified by a combustion state index, a combustion state regulation method is proposed to find the optimal regulation path of system parameters. Active subspace method is further applied to shorten the regulation step by identifying the active direction. The proposed method and findings are useful for optimal regulation of burning LCV gases in industrial burners.     

Benchmark experiment of large-angle scattering reaction cross section of iron at 14 MeV using two shadow bars – Comparison of experimental results with ENDF/B-VIII –

ABSTRACT

It is important to perform neutron transport simulations with accurate nuclear data in the neutronics design of a fusion reactor. However, absolute values of large-angle scattering cross sections vary among nuclear data libraries even for well-examined nuclide of iron. Benchmark experiments focusing on large-angle scattering cross sections were thus performed to confirm the correctness of nuclear data libraries. The series benchmark experiments were performed at a DT neutron source facility, OKTAVIAN of Osaka University, Japan, by the unique experimental system established by the authors’ group, which can extract only the contribution of large-angle scattering reactions. This system consists of two shadow bars, target plate (iron), and neutron detector (niobium). Two types of shadow bars were used and four irradiations were conducted for one experiment, so that contribution of room-return neutrons was effectively removed and only large-angle scattering neutrons were extracted from the measured four Nb reaction rates. The obtained experimental results were compared with calculations for five nuclear data libraries including JENDL-4.0, JEFF.-3.3, FENDL-3.1, ENDF/B- VII, and recently released ENDF/B-VIII. It was found from the comparison that ENDF/B-VIII showed the best result, though ENDF/B-VII showed overestimation and others are in large underestimation at 14 MeV.     

Process Intensification of Living Cationic Polymerization of Isobutylene by a Flow Reaction System

Increasing the reaction temperature of the living cationic polymerization of isobutylene is crucial for industrial production due to the cost of refrigeration. The reaction temperature increase was achieved with an accelerated reaction rate using a flow reaction system. The polymerization conditions, including the flow reactor design, were based on the results of kinetic studies. Utilizing a milli‐scale flow reactor, polyisobutylene, which has a narrow molecular weight distribution, was obtained within a considerably short residence time at a high temperature. Furthermore, it was confirmed that the value of M_w/M_n correlates with the product of the Reynolds number and the angle of collision.     

Synthesis,characterization, and visible-light photocatalytic activity of transition metals doped ZTO nanoparticles

Transition metals doping has been proved to be a feasible way for tuning the physical properties on the surface and bulk of nanomaterials and also for the good performance in decontamination of emerging pollutants. In this context, doped samples of zinc tin oxide or zinc stannate nanoparticles (ZTO NPs) by several transition metals were synthesized in order to enhance the optical absorbance with the aims of reducing the band gap and therefore ameliorated their photocatalytic activity. They were characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy, Raman spectroscopy and photoluminescence. The XRD patterns and the microscopic observations showed the formation of spherical nanoparticles with an average size of about 30 nm and highly pure ZTO phase with an inverse spinel structure. The Raman spectra were dominated by bands relatives to the F2g (2) and A1g symmetries modes of inverse spinel structure. The band gap Eg is estimated to be 3.75 eV for the undoped sample, and 3.67, 3.64, 3.78 and 3.21 eV, for 2% Fe, 2% Mg, 2% Gd, and 2% Mn doped ZTO samples, respectively.Furthermore, the undoped ZTO NPs have the intrinsic problem of recombination of photogenerated charge carriers. We have shown that the reduction of the band gap and oxygen vacancies resulting from the doping effect could be a useful tool for trapping and avoid the recombination of electrons coming from photosensitized rhodamine B (RhB) under visible light irradiation. Owing to the structural advantages and low band gap, 2% Mn doped ZTO NPs, with the kinetic rate constants k of 0.024 min⁻¹, show enhanced performance for the elimination of RhB in aqueous solution compared to undoped and other doped ZTO NPs.     

Comparison of co-current and counter-current flow in a bifunctional reactor containing ammonia synthesis and 2-butanol dehydrogenation to MEK

In this study, a multi-tubular thermally coupled packed bed reactor in which simultaneous production of ammonia and methyl ethyl ketone (MEK) takes place is simulated. The simulation results are presented in two co-current and counter-current flow modes. Based on this new configuration, the released heat from the ammonia synthesis reaction as an extremely exothermic reaction in the inner tube is employed to supply the required heat for the endothermic 2-butanol dehydrogenation reaction in the outer tube. On the other hand, MEK and hydrogen are produced by the dehydrogenation reaction of 2-butanol in the endothermic side, and the produced hydrogen is used to supply a part of the ammonia synthesis feed in the exothermic side. Thus, 30.72% and 31.88% of the required hydrogen for the ammonia synthesis are provided by the dehydrogenation reaction in the co-current and counter-current configurations, respectively. Also, according to the thermal coupling, the required cooler and furnace for the ammonia synthesis and 2-butanol dehydrogenation conventional plants are eliminated, respectively. As a result, operational costs, energy consumption and furnace emissions are considerably decreased. Finally, a sensitivity analysis and optimization are applied to study the effect of the main process parameters variation on the system performance and obtain the minimum hydrogen make-up flow rate, respectively.     

Evaluation of hydrodynamic behavior of the perforated gas distributor of industrial gas phase polymerization reactor using CFD-PBM coupled model

A 2D computational fluid dynamics (Eulerian–Eulerian) multiphase flow model coupled with a population balance model (CFD-PBM) was implemented to investigate the fluidization structure in terms of entrance region in an industrial-scale gas phase fluidized bed reactor. The simulation results were compared with the industrial data, and good agreement was observed. Two cases including perforated distributor and complete sparger were applied to examine the flow structure through the bed. The parametric sensitivity analysis of time step, number of node, drag coefficient, and specularity coefficient was carried out. It was found that the results were more sensitive to the drag model. The results showed that the entrance configuration has significant effect on the flow structure. While the dead zones are created in both corners of the distributors, the perforated distributor generates more startup bubbles, heterogeneous flow field, and better gas–solid interaction above the entrance region due to jet formation.     

Studying local liquid velocity in liquid–solid packed bed using the newly developed X-ray DIR technique

Combination of X-ray Digital Industrial Radiography (DIR) and Particle Tracking Velocimetry (PTV) techniques for local liquid velocity measurement (V_LL) has been newly developed and successfully applied for trickle bed reactor (TBR). The technique was validated against newly developed fiber optical probe technique. This work attempts to highlight the applicability of this newly developed technique on a liquid–solid packed bed reactor. In this work, liquid was represented by water and solids were represented by EPS beads. The EPS beads were chosen because of its low density property. Three superficial liquid velocities (V_SL) were applied to the system. The experiment was replicated four times. The digital industrial radiography (DIR) consists of a complementary metal oxide semiconductor (CMOS) digital detector and X-ray source. Results of this work suggest that the technique has been successfully applied and comparable with previous work that has been done in the literature. It also suggests that there will be a maximum measurable interstitial liquid velocity when it travel inside the packed bed. The measured V_LL can have a maximum range that is between 4 and 4.7 times that of its V_SL. For V_SL=0.42±±2%, the V_LL-Max is in between 1.7 cm/s and 1.9 cm/s, V_SL=0.84±±2%, the V_LL-Max is in between 3.6 cm/s and 4.0 cm/s, and for V_SL=1.11±±2%, the V_LL-Max is in between 4.3 cm/s and 4.8 cm/s.     

Copper–4,4′-dipyridyl coordination compound as solid reagent for spectrophotometric determination of reducing sugar employing a multicommutation approach

In this work a multicommuted flow system employing copper–4,4′- dipyridyl coordination compound as the solid-phase reagent for the spectrophotometric determination of reducing sugar was developed. The coordination compound was synthesized through a reaction of the 4,4′-dipyridyl and copper (II) nitrate, under hydrothermal conditions. The complex was characterized by infrared spectroscopy (FTIR), power X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and thermogravimetric analysis (TGA). Based on the characterization, a multicommuted spectrophotometric procedure for the determination of reducing sugar using copper (II) complex as solid reagent is proposed. The proposed method was based on the redox reaction between a monosaccharide, such as fructose and glucose (reducing sugar) and Cu(II). This reaction, mediated in an alkaline medium, produces a yellow compound that can be determined by absorption electronic spectroscopy (λ_ABS = 420 nm). Under optimum experimental conditions, a linear response ranging from 1.0 to 20.0 g L⁻¹ (R = 0.9978 and n = 5), a detection (3σ criterion) and quantification (10σ criterion) limit estimated at 0.23 and 0.75 g L⁻¹, respectively, a standard deviation relative of 4.7% (n = 7), for a reference solution of 10.0 g L⁻¹ reducing sugar, and a sampling rate of 75 determinations per hour were achieved. The proposed system was applied to the determination of reducing sugars in coconut water and juices. The analysis of ten samples and the application of the t-test to the results found, and those obtained using reference procedures (AOAC), provided no significant differences at a 95% confidence level. This system enabled the analysis of reducing sugar with ease and simplicity, providing a significant economy of the solid reagent (600 μg per determination) and reducing effluent generation.