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.     

Nanotechnology‐based wastewater treatment

Water contamination is a global challenge impacting both the environment and human health with significant economic and social costs. The growing scarcity of usable water resources requires effective treatment of wastewater. In this context, developing cheaper, safer and more efficient wastewater treatment technologies are the need of the hour. One promising approach that several studies have reported success has been the usage of nanomaterials in water and waste water management. The rapid progress of research in nanomaterial sciences has shown their growing potential; however, there has not been a great amount of information available on their implementation. This review focuses on developments in nanotechnology that hold strong potential for wastewater treatment. The review covers key techniques in nanomaterial‐based water treatments including adsorption, filtration and photocatalysis with recent examples showing how to improve their properties and efficiencies according to the need.     

Preparation of high-activity coal char-based catalysts from high metals containing coal gangue and lignite for catalytic decomposition of biomass tar

The potential of using high metals containing coal gangue and lignite to prepare high-activity coal char-based catalysts is investigated for effective biomass tar decomposition. Loose structure and rough surface are formed for these char-based catalysts with heterogeneous distribution of a large number of inorganic particles. In the biomass tar decomposition, the performance of the coal char-based catalysts is significantly influenced by the content of the metals in the raw materials and coal gangue char (GC) with the ash content as high as 50.80% exhibits the highest activity in this work. A high biomass tar conversion efficiency of 93.5% is achieved at 800 °C along with a significant increase in the fuel gas product. During the five-time consecutive tests, the catalytic performance of GC increases a little at the second or third times reuse and remains relatively stable, showing the remarkable stability of the catalyst in biomass tar decomposition applications.     

Operation of Rh/Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl wire mesh honeycomb catalytic modules in diesel steam and autothermal reforming

The Rh/Ce_0·75Zr_0·25O_2–δ-ƞ-Al₂O₃/FeCrAl structured catalytic blocks of length 10, 20, and 60 mm were prepared and tested in the reactions of steam and autothermal reforming of n-hexadecane. It was found in a series of experiments on hexadecane steam reforming with the catalyst heating solely through the reactor wall that the complete conversion of hexadecane at a furnace temperature below 750 °C was not achieved even at GHSV = 10,000 h⁻¹. Under these conditions, the formation of carbon on the catalyst surface was observed. At the reactor wall temperature of 800 °C, the complete conversion of hexadecane was achieved even in the 10 mm long catalytic block (GHSV = 60,000 h⁻¹), accompanied by the formation of various intermediate light hydrocarbons. To achieve complete conversion of these intermediate compounds (mainly 1-alkenes), it is necessary to carry out the steam reforming reaction at GHSV = 10,000 h⁻¹. At hexadecane autothermal reforming, heat is supplied to the reaction zone by exothermic oxidation reaction, which makes this process more efficient. In experiments with the use of additional external heat supply through the reactor wall, complete conversion of hexadecane occurred at GHSV = 120,000 h⁻¹. To convert all by-products (mainly 1-alkenes) and achieve a nearly thermodynamic equilibrium distribution of the main reaction products (H₂, CO, CO₂), the reaction should be carried out at GHSV = 20,000 h⁻¹. Without external heat supply, hexadecane conversion decreased, while the content of light hydrocarbons in the reaction products increased. An increase in the inlet amount of oxygen helps to compensate the heat losses in the reactor and to increase the efficiency of hexadecane autothermal reforming. The performed experiments allow better understanding of the processes which occur during the steam and autothermal reforming of diesel.     

Laser-assisted preparation of monolithic acidic catalysts for biomass conversion

5-(Hydroxymethyl)furfural (5-HMF) is a vital platform molecule from which a variety of high-value-added fine chemicals and polymerizable monomers can be prepared. The use of solid acids to catalyze the conversion of biomass into 5-HMF is environmentally friendly and economical. However, exploiting the high yield of 5-HMF in a highly concentrated reactant system is challenging. Herein, we present a laser-assisted method for preparing highly acidic monolithic acidic catalysts. A monolithic acidic catalyst based on metal Zr sheets was synthesized and used to catalytically convert 30 wt% fructose into 5-HMF (conversion rate: 96%; yield: 95%). The catalyst was immediately separated from the reaction solution by direct removal at the end of the reaction. Catalytic efficiency was largely unaffected after 10 cycles of use, and the same catalytic efficiency was observed after laser-regeneration, highlighting the potential industrial applicability of the developed catalyst.     

渣油催化临氢热转化钼铁双金属催化剂的研究

Replacement of precious single metal catalysts with cost-effective, highly-dispersed composite catalysts for catalytic hydrothermal conversion of residue holds tremendous promise for the residue upgrading technologies. Organic metals were added to the feed as the oil-soluble precursors, and transformed into the catalytic active phases in this work. Physical properties and structures of the composite catalysts had been investigated by X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope and transmission electron microscopy. The composite catalysts were found to be highly efficient in the catalytic hydrothermal conversion of both model compound and residue. Increased metal dispersion and synergistic effects of two metals played indispensable roles in such catalytic system. Results showed that under the test conditions in the article, the catalyst had the best catalytic performance when the mass ratio of molybdenum to iron was 1.5.     

Hydrogen production by oxidative steam reforming of methanol over anodic aluminum oxide-supported Cu-Zn catalyst

Oxidative steam reforming of methanol (OSRM), which is a convenient reaction for producing hydrogen, suffers from the hot spot formation problem when conventional particle catalysts are used. Recently, an anodic aluminum oxide (AAO)-supported Cu-Zn catalyst was proposed as an OSRM catalyst for its high thermal conductivity through the aluminum metal body. In this study, OSRM was conducted in a prototype reactor packed with the AAO plate catalyst strips. It was verified that the high thermal conductivity of the catalyst effectively suppresses the hot spot formation and makes the temperature profile smooth along the reactor. The start-up time of the reactor depended on the preheating temperature and was very short (less than 2 min) for preheating over 503 K. The methanol conversion and reactor temperature increased with increasing O₂/CH₃OH mole ratio, indicating that the mole ratio can be used as a control variable to operate the reactor at desired conditions. Further, a reactor model was developed and verified, and the simulation showed that for a given total reactor volume, an optimal reactor configuration could be achieved by shortening the reactor length while widening the cross-sectional area.     

电感耦合等离子体原子发射光谱法测定辛酸铑催化剂中铂钯铅铁铜铝镍

准确测定辛酸铑催化剂中杂质元素含量,是判定产品是否合格的重要指标之一。以往常采用直流电弧发射光谱法(摄谱法)进行检测,但测定周期长,且重复性较差。用电感耦合等离子体原子发射光谱法(ICP-AES)测定辛酸铑催化剂中微量杂质元素时,辛酸铑催化剂样品中含有的大量有机组分和铑基体会对测定有严重干扰。实验采用反复滴加硝酸消解样品中有机组分,再用王水溶解盐类,选用合适背景点扣除的方式消除铑基体的干扰,建立了使用ICP-AES测定辛酸铑催化剂中0.001%~0.1%(质量分数)Pt、Pd、Pb、Fe、Cu、Al、Ni等7种微量杂质元素的方法。各元素在0.10~10.00μg/mL范围内与其发射强度呈线性关系,相关系数均大于0.9999;方法检出限(μg/mL)为0.075(Pt)、0.0033(Pd)、0.015(Pb)、0.0036(Fe)、0.010(Cu)、0.001(Al)、0.012(Ni)。实验方法用于测定辛酸铑催化剂样品中Pt、Pd、Pb、Fe、Cu、Al、Ni,结果的相对标准偏差为(RSD,n=7)为1.4%~9.6%。按照实验方法测定辛酸铑催化剂中Pt、Pd、Pb、Fe、Cu、Al、Ni,并与直流电弧发射光谱法的测定结果进行比对,结果相一致。     

Metal sulfate decomposition using green Pd-based catalysts supported on γAl2O3 and SiC: A common step in sulfur-family thermochemical cycles

Thermochemical water splitting cycles (TWSCs) are processes with the potential for large-scale production of carbon-free hydrogen. Among these, the sulfur-family thermochemical cycles are considered the most promising due to both, the use of readily affordable chemical reagents and the temperature required to thermally decompose oxygenated sulfur compounds, which is achievable by solar means. Indeed, solar heat assisted metal sulfate decomposition is a key step, where catalysis can be employed to reduce decomposition temperature. Here we present a green route to synthesize Ag-Pd and Fe-Pd intermetallic alloy catalysts supported over γ-Al₂O₃ and Si-C by a microwave-assisted method using glycerol both as a solvent and as a reducing and stabilizing agent. The obtained supported catalysts were physicochemically characterized. Fe-Pd/Al₂O₃ catalyst exhibited the best performance, abating the zinc sulfate decomposition temperature by ca. 85 °C in comparison with other reported catalysts.