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.     

Sustainable ammonia production through process synthesis and global optimization

Current ammonia production technologies have a significant carbon footprint. In this study, we present a process synthesis and global optimization framework to discover the efficient utilization of renewable resources in ammonia production. Competing technologies are incorporated in a process superstructure where biomass, wind, and solar routes are compared with the natural gas-based reference case. A deterministic global optimization-based branch-and-bound algorithm is used to solve the resulting large-scale nonconvex mixed-integer nonlinear programming problem (MINLP). Case studies for Texas, California, and Iowa are conducted to examine the effects of different feedstock prices and availabilities. Results indicate that profitability of ammonia production is highly sensitive to feedstock and electricity prices, as well as greenhouse gas (GHG) restrictions. Under strict 75% GHG reductions, biomass to ammonia route is found to be competitive with natural gas route, whereas wind and solar to ammonia routes require further improvement to compete with those two routes. © 2018 American Institute of Chemical Engineers AIChE J, 65: e16498 2019     

Simultaneous enhancement of the efficiency and stability of organic solar cells using PEDOT:PSS grafted with a PEGME buffer layer

We report a simple processing method to simultaneously improve the efficiency and stability of organic solar cells (OSCs). Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxy-thiophene (PEDOT:PSS), widely used as hole transport layer (HTL) in OSCs, tends to accelerate the degradation of devices because of its hygroscopic and acidic properties. In this regard, we have modified PEDOT:PSS to reduce its hygroscopic and acidic properties through a condensation reaction between PEDOT:PSS and poly(ethylene glycol) methyl ether (PEGME) in order to improve the efficiency and stability of OSCs. As a result, the power conversion efficiency (PCE) increased by 21%, from 2.57% up to 3.11%. A better energy level alignment by the reduced work function of the modified PEDOT:PSS with a highest occupied molecular orbital (HOMO) level of poly(3-hexylthiophene-2,5-diyl) (P3HT) is considered the origin of the improved the efficiency. The half-life of OSCs with PEDOT:PSS modified with PEGME buffer layer also increased up to 3.5 times compared to that of devices with pristine PEDOT:PSS buffer layer.     

Structural and optical properties of CdTe-nanocrystals thin films grown by chemical synthesis

By mans of a chemical synthesis technique stoichiometric CdTe-nanocrystals thin films were prepared on glass substrates at 70 °C. First, Cd(OH)₂ films were deposited on glass substrates, then these films were immersed in a growing solution prepared by dissolution of Te in hydroxymethane sulfinic acid to obtain CdTe. The structural analysis indicates that CdTe thin films have a zinc-blende structure. The average nanocrystal size was 19.4 nm and the thickness of the films 170 nm. The Raman characterization shows the presence of the longitudinal optical mode and their second order mode, which indicates a good crystalline quality. The optical transmittance was less than 5% in the visible region (400–700 nm). The compositional characterization indicates that CdTe films grew with Te excess.     

（S）-噻吗洛尔半水合物的合成及表征

为了开发β受体阻断剂新药（S）-噻吗洛尔半水合物，采用3-吗啉-4-氯-1，2，5-噻二唑为起始原料，经水解反应得到中间体1（3-吗啉-4-羟基-1，2，5-噻二唑）。中间体1与R-环氧氯丙烷发生醚化反应，经后处理及重结晶得到中间体2 {（R）-4-［4-（环氧乙烷-2-基甲氧基）-1，2，5-噻二唑-3-基］吗啉}。中间体2经胺化反应、马来酸成盐及重结晶得到（S）-马来酸噻吗洛尔。（S）-马来酸噻吗洛尔经游离、纯水转晶得到符合药典标准的（S）-噻吗洛尔半水合物，总收率14.05%且e.e.值为99.66%。最终成品经IR、1H-NMR、13C-NMR、MS、TGA、DSC表征，并优化各步反应条件。结果表明:以三乙胺为醚化反应缚酸剂75 ℃反应最佳；以乙醇为胺化反应溶剂46 ℃反应16 h最佳；S-噻吗洛尔的转晶拆分以水作溶剂，比传统不对称合成工艺安全稳定，操作简单，适合工业化生产。     

Synthesis and Characterization of Co Nanocomposite Based on Poly(benzimidazole-amide) Matrix and Their Behavior as Catalyst in Oxidation Reaction

2,6-Bis(5-amino-1H-benzimidazol-2-yl)pyridine was prepared and characterized by Fourier transform infrared spectroscopy, elemental analysis, ¹H-NMR, and ¹³C-NMR spectroscopic methods. Then a new poly(benzimidazole-amide) was synthesized by polymerization of the corresponding diamine and isophthalic acid. The obtained poly(benzimidazole-amide) exhibited good yield and high thermal stability. Due to the existence of benzimidazole moieties in polymer’s structure, it has the tendency to form complexes with metal ions. So, a new poly(benzimidazole-amide)/Co nanocomposite was prepared. Morphological studies revealed that metal nanoparticles were dispersed in the polymer matrix without any aggregation. poly(benzimidazole-amide)/Co nanocomposite was used as a catalyst in the oxidation of ethyl benzene to acetophenone with tert-butyl hydroperoxide.     

Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

Design of functionalized α-Fe2O3 (III) films with long-term anti-wetting properties

The design of functional anti-wetting ceramic coatings is always a bottleneck restricting the development of ceramic techniques. This study proposes a liquid phase synthesis method to fabricate α-Fe₂O₃ (III) ceramic powders with promising applications and introduces a facile electrophoretic deposition (EPD) technique to construct the corresponding functionalized hydrophobic films – superhydrophobic functionalized α-Fe₂O₃ ceramic films (SFOFS) with roughly even distribution and a high water contact angle (CA) of 169°±1° – followed by heat posttreatments. The microtopography and crystalline structures of the product were investigated by FESEM, EDX, and XRD techniques. The EPD controllability of SFOFS was studied by adjusting the EPD time and the applied field strengths. In addition, the SFOFS show excellent long-term anti-wetting properties for twenty-four months after undergoing a series of tests, including soaking, water droplet impacting, immersion by droplets with different surface tensions and exposure to different gases and relative humidity conditions, etc. This study substantially helps the design of other kinds of functional anti-wetting films through the proposed convenient method beyond the oxide limit.     

Simultaneous synthesis of a heat exchanger network with multiple utilities using utility substages

Heat exchanger network synthesis (HENS) has progressed by using mathematical programming-based simultaneous methodology. Although various considerations such as non-isothermal mixing and bypass streams are applied to consider real world alternatives in modeling phase, many challenges are faced because of its properties within non-convex mixed-integer nonlinear programming (MINLP). We propose a modified superstructure, which contains a utility substage for use in considering multiple utilities in a simultaneous MINLP model. To improve model size and convergence, fixed utility locations according to temperature and series connections between utilities are suggested. The numbers of constraints, discrete, and continuous variables show that overall model size decreases compared with previous research. Thus, it is possible to expand the feasible search area for reaching the nearest global solution. The model's effectiveness and applications are exemplified by several literature problems, where it is used to deduce a network superior to that of any other reported methodology.