Enhancing gas phase Fischer-Tropsch synthesis catalyst design

This paper presents the results on the research in the development of a Fe-based catalyst with Co as a co-catalyst, and Ru and ZnO as promoters. The catalytic performance of these materials for FT synthesis was investigated in the gas phase employing a fixed bed reactor system. The Fe-Zn-K/γ-Al₂O₃ catalyst performance was used as the benchmark. The data show that by varying the process conditions (T, P, flow rate), it is possible to achieve a narrow distribution of the liquid products. The effect of co-catalysts and promoters such as K and Zn are also presented. The results from a series of Fe₄Co₁Zn_0.04 based catalysts for Fischer-Tropsch (FT) synthesis, in which the different amounts of Ru are incorporated showed that the addition of Ru suppressed the CH₄ formation at the cost of increasing the CO₂ selectivity. The newly designed catalysts showed significantly high activity towards CO conversion (>70%), along with low selectivity towards CO₂ (5-15%) and methane (ND - 3%). It is also shown that the support material plays a role in the selectivities obtained.     

室温离子液体——一种新型的绿色溶剂与催化剂

室温离子液体作为一种相对友好的溶剂和催化剂体系正在被人们认识和接受。室温离子液体作为反应介质或催化剂具有更宽的液态范围和几乎可以忽略的蒸汽压,并且可以重复使用,这在环境问题日益引起人们关注的今天显得尤为重要。室温离子液体作为反应介质,可以促进反应,它本身也可以作为催化剂,特别是氯铝酸离子液体,对某些反应表现出比传统无机酸更好的催化活性;室温离子液体具有良好的溶解性,可以用做萃取剂,在一些均相反应过程中,由于室温离子液体的加入,可以构成两相体系,有利于产物的分离。作为一类绿色、新型的溶剂和催化剂,室温离子液体具有广泛的应用前景。     

State-of-the-art technology: Recent investigations on laser-mediated synthesis of nanocomposites for environmental remediation

In both developing and industrialized/developed countries, various hazardous/toxic environmental pollutants are entering water bodies from organic and inorganic compounds (heavy metals and specifically dyes). The global population is growing whereas the accessibility of clean, potable and safe drinking water is decreasing, leading to world deterioration in human health and limitation of agricultural and/or economic development. Treatment of water/wastewater (mainly industrial water) via catalytic reduction/degradation of environmental pollutants is extremely critical and is a major concern/issue for public health. Light and/or laser ablation induced photocatalytic processes have attracted much attention during recent years for water treatment due to their good (photo)catalytic efficiencies in the reduction/degradation of organic/inorganic pollutants. Pulsed laser ablation (PLA) is a rather novel catalyst fabrication approach for the generation of nanostructures with special morphologies (nanoparticles (NPs), nanocrystals, nanocomposites, nanowires, etc.) and different compositions (metals, alloys, oxides, core-shell, etc.). Laser ablation in liquid (LAL) is generally considered a quickly growing approach for the synthesis and modification of nanomaterials for practical applications in diverse fields. LAL-synthesized nanomaterials have been identified as attractive nanocatalysts or valuable photocatalysts in (photo)catalytic reduction/degradation reactions. In this review, the laser ablation/irradiation strategies based on LAL are systematically described and the applications of LAL synthesized metal/metal oxide nanocatalysts with highly controlled nanostructures in the degradation/reduction of organic/inorganic water pollutants are highlighted along with their degradation/reduction mechanisms.     

Quadruplex-Templated and Catalyzed Ligation of Nucleic Acids

Template-guided chemical reactions between nucleic acid strands are an important process in biomedical research. However, almost all of these reactions employ an oligonucleotide-templated approach that is based on the double-helix alignment. The moderate stability of the double helix makes this approach unsuitable for many chemical reactions, so alternative nucleic acid alignment mechanisms, demonstrating higher thermal and chemical stability, are desirable. Earlier, we described a noncovalent coupling mechanism between DNA strands through a quadruplex-and-Mg²⁺ connection (QMC). QMC is based on G-quadruplexes and allows unusually stable and specific interactions. Herein, a novel catalytic nucleic acid reaction, based on QMC, is described. This approach uses G-tetrads as a structural and recognition element without employing Watson-Crick complementarity rules at any stage of substrate/catalyst formation or interaction between them. Quadruplex-templated ligation can be achieved through the self-ligation of two nucleic acid strands, or through a quadruplex catalyst, which forms a G-triplex and specifically connects the strands. The process is extraordinarily robust and efficient. For instance, the ligation of carbodiimide-activated substrates can proceed in boiling solutions, and complete ligation is demonstrated within a minute. The quadruplex-templated and catalyzed reactions will create new opportunities for chemical reactions requiring harsh experimental conditions.     

Review on synthesis of porous TiO2-based catalysts for energy conversion systems

Porous TiO₂-based catalysts have recently received remarkable attention in the field of energy conversion systems, including hydrogen/oxygen evolution reaction, oxygen/nitrogen reduction reaction, and photodegradation of pollutants owing to their unique structure, large surface area, and good chemical stability. In this report, we review existing research on porous TiO₂-based catalysts for energy conversion systems during the past four years. First, the advantages of porous TiO₂-based catalysts are introduced. Next, the synthetic approaches in developing porous TiO₂-based catalysts are summarized. The different types of energy conversion systems based on porous TiO₂-based catalysts are then presented. Finally, the challenges and future perspectives in synthesizing porous TiO₂-based catalysts are discussed.     

Direct thermochemical liquefaction of microcrystalline cellulose by sub- and supercritical organic solvents

Direct thermochemical liquefaction of microcrystalline cellulose was carried out using sub- and supercritical solvents in a batch reactor. The decomposition efficiency of dodecane and m-xylene widely used in petrochemical industries was compared to that of methanol and 1,4-dioxane. At 400 °C, the conversion in methanol was the highest (92 wt% including gaseous products), but the operating pressure was too high. m-Xylene at the same temperature showed the conversion of 71.5 wt% with a lower number of products and milder pressure. Hydrogen contributed to the increase of the total conversion by 3–8% in m-xylene and methanol, compared with the results without adding any additional gas or with nitrogen pressurization. An acid-modified silica catalyst led to a significant increase of conversion in the supercritical methanol, but its effect was negligible in the aprotic solvents. The product compounds and property of solid residue depended on the supercritical solvents applied. The thermal-treated char after liquefaction in m-xylene, dodecane and 1,4-dioxane was an effective adsorbent for CO₂ adsorption, showing the level comparable with activated carbons.     

Development of new high-throughput screening method to compare and to detect efficient catalysts for adhesive materials

Organotin compounds particularly dibutyltin dilaurate, are commonly used as catalysts in coatings or adhesive materials to crosslink silyl modified polymers. However, environmental concerns should lead before 2020 to ban organotin compounds due to their high toxicity. Thus new catalysts must be developed. According to the different types of catalytic systems, i.e. acid, basic or metal containing catalysts, a large variety of candidates should be tested. Thus a high-throughput screening (HTS) method could be an interesting tool for the detection of new efficient catalysts to substitute organotin compounds. We report a global HTS method, compatible with organic amino or acid catalysts libraries, as well as with metal-containing libraries.     

Microprocessor controlled three-way catalyst efficiency monitoring system

The present paper describes a new design for a microcontrolled three-way catalyst efficiency monitoring system. The system is based on the Motorola 68HC11e2 microprocessor and utilizes the differential signal from a pair of thermocouples installed at the catalyst outlet and inlet sections. This signal is processed in real time using an appropriate statistical algorithm and the corresponding results are compared to experimentally determined limiting values to assess the current state of the catalyst efficiency during driving conditions. The result of this comparison is presented on an LCD display as an A, B, C, or FAIL catalyst condition signal. The system can be readily installed and can operate on new and used cars provided that the type of catalyst used has been experimentally tested to provide the necessary limiting values that characterize its relative levels of efficiency. It can also be reprogrammed and calibrated via a RS232C serial interface.     

Dynamic Simulation and Optimization of a Dual‐Type Methanol Reactor Using Genetic Algorithms

In this investigation, a dynamic simulation and optimization for an auto‐thermal dual‐type methanol synthesis reactor was developed in the presence of catalyst deactivation. Theoretical investigation was performed in order to evaluate the performance, optimal operating conditions, and enhancement of methanol production in an auto‐thermal dual‐type methanol reactor. The proposed reactor model was used to simulate, optimize, and compare the performance of a dual‐type methanol reactor with a conventional methanol reactor. An auto‐thermal dual‐type methanol reactor is a shell‐and‐tube heat exchanger reactor in which the first reactor is cooled with cooling water and the second one is cooled with synthesis gas. The proposed model was validated against daily process data measured of a methanol plant recorded for a period of 4 years. Good agreement was achieved. The optimization was achieve by use of genetic algorithms in two steps and the results show there is a favorable profile of methanol production rate along the dual‐type reactor relative to the conventional‐type reactor. Initially, the optimal ratio of reactor lengths and temperature profiles along the reactor were obtained. Then, the approach was followed to get an optimal temperature profile at three periods of operation to maximize production rate. These optimization approaches increased by 4.7 % and 5.8 % additional yield, respectively, throughout 4 years, as catalyst lifetime. Therefore, the performance of the methanol reactor system improves using optimized dual‐type methanol reactor.     

Magnetically recyclable Fe-Ni alloy catalyzed dehydrogenation of ammonia borane in aqueous solution under ambient atmosphere

In this work, we report a very simple method to in situ prepare the Fe_1−xNi_x (x = 0, 0.3, 0.4, 0.5, 0.7 and 1) nano-alloys as the catalysts for H₂ generation from the aqueous NH₃BH₃ solution under ambient atmosphere at room temperature. The prepared nano-alloys possess Pt-like high catalytic activity, especially for the specimen of Fe_0.5Ni_0.5, with which the hydrolysis of NH₃BH₃ would totally complete in only 2.2 min. Moreover, these catalysts can be easily magnetically separated for recycle purpose, and can almost keep the same high activity even after 5 times of recycle under ambient atmosphere. Such alloy catalysts are expected to be useful for fuel cells, metal-air batteries and electrochemical sensors. Moreover, the concepts behind these preliminary results present a wide range of possibilities for the further development of synthesis of air and water-stable magnetic nano-alloys.