Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

Daidzein has been widely used in pharmaceuticals,nutraceuticals,cosmetics,feed additives,etc.Its preparation process and related reaction mechanism need to be further investigated.A cost-effective process for synthesizing daidzein was developed in this work.In this article,a two-step synthesis of daidzein(Friedel–Crafts acylation and[5+1]cyclization)was developed via the employment of trifluoromethanesulfonic acid(TfOH)as an effective promoting reagent.The effect of reaction conditions such as solvent,the amount of TfOH,reaction temperature,and reactant ratio on the conversion rate and the yield of the reaction,respectively,was systematically investigated,and daidzein was obtained in 74.0%isolated yield under optimal conditions.Due to the facilitating effect of TfOH,the Friedel–Crafts acylation was completed within 10 min at 90℃ and the[5+1]cyclization was completed within 180 min at 25℃.In addition,a possible reaction mechanism for this process was proposed.The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Process synthesis for the separation of coal-to-ethanol products

The coal-to-ethanol process,as the clean coal utilization,faces challenges from the energy-intensive distillation that separates multi-component effluents for pure ethanol.Referring to at least eight columns,the synthesis of the ethanol distillation system is impracticable for exhaustive comparison and difficult for conventional superstructure-based optimization as rigorous models are used.This work adopts a superstructure-based framework,which combines the strategy that adaptively selects branches of the state-equipment network and the parallel stochastic algorithm for process synthesis.High-performance computing significantly reduces time consumption,and the adaptive strategy substantially lowers the complexity of the superstructure model.Moreover,parallel computing,elite search,population redistribution,and retention strategies for irrelevant parameters are used to improve the optimization efficiency further.The optimization terminates after 3000 generations,providing a flowsheet solution that applies two non-sharp splitting options in its distillation sequence.As a result,the 59-dimension superstructure-based optimization was solved efficiently via a differential evolution algorithm,and a high-quality solution with a 28.34%lower total annual cost than the benchmark was obtained.Meanwhile,the solution of the superstructure-based optimization is comparable to that obtained by optimizing a single specific configuration one by one.It indicates that the superstructure-based optimization that combines the adaptive strategy can be a promising approach to handling the process synthesis of large-scale and complex chemical processes.

Optimal synthesis of heat-integrated distillation configurations using the two-column superstructure

In the realm of the synthesis of heat-integrated distillation configurations,the conventional approach for exploring more heat integration possibilities typically entails the splitting of a single column into a twocolumn configuration.However,this approach frequently necessitates tedious enumeration procedures,resulting in a considerable computational burden.To surmount this formidable challenge,the present study introduces an innovative remedy:The proposition of a superstructure that encompasses both single-column and multiple two-column configurations.Additionally,a simultaneous optimization algorithm is applied to optimize both the process parameters and heat integration structures of the twocolumn configurations.The effectiveness of this approach is demonstrated through a case study focusing on industrial organosilicon separation.The results underscore that the superstructure methodology not only substantially mitigates computational time compared to exhaustive enumeration but also furnishes solutions that exhibit comparable performance.

Catalytic kinetics of dimethyl ether one-step synthesis over CeO_2–CaO–Pd/HZSM-5 catalyst in sulfur-containing syngas process

CeO_2–CaO–Pd/HZSM-5 catalyst was prepared for the dimethyl ether(DME) one-step synthesis in a continuous fixed-bed micro-reactor from the sulfur-containing syngas. The catalytic stability over hybrid catalyst of CeO_2–CaO–Pd/HZSM-5 was investigated to ensure that the kinetics experimental results were not significantly influenced by induction period and catalytic deactivation. A large number of kinetic data points(40 sets) were obtained over a range of temperature(240–300 °C), pressure(3–4 MPa), gas hourly space velocity(GHSV)(2000–3000 L·kg^(-1)·h^(-1)) and H_2/CO mole ratio(2–3). Kinetic model for the methanol synthesis reaction and the dehydration of methanol were obtained separately according to reaction mechanism and Langmuir–Hinshelwood mechanism. Regression parameters were investigated by the method combining the simplex method and Runge–Kutta method. The model calculations were in appropriate accordance with the experimental data.

Effects of Co_3O_4 nanocatalyst morphology on CO oxidation:Synthesis process map and catalytic activity

This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies（i.e.,nanorods,nanosheets,and nanocubes） were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures（≤ 140℃）.Nanorods can be synthesized in CoCl2 solution,while Co（NO3）2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature（higher than 140 ℃） results in the formation of nanocubes in either Co（NO3）2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^（3＋） on the surface,much higher reducibility,and better oxygen desorption capacity.

Developing super-hydrophobic and corrosion-resistant coating on magnesium-lithium alloy via one-step hydrothermal processing

Formation of super-hydrophobic and corrosion-resistant coatings can provide significant corrosion protection to magnesium alloys.However,it remains a grand challenge to produce such coatings for magnesium-lithium alloys due to their high chemical reactivity.Herein,a one-step hydrothermal processing was developed using a stearic-acid-based precursor medium,which enables the hydrothermal conversion and the formation of low surface energy materials concurrently to produce the super-hydrophobic and corrosion-resistant coating.The multiscale microstructures with nanoscale stacks and microscale spheres on the surface,as well as the through-thickness stearates,lead to the super-hydrophobicity and excellent corrosion resistance of the obtained coating.

One-step synthesis of Pt@ZIF-8 catalyst for the selective hydrogenation of 1,4-butynediol to 1,4-butenediol

A catalyst consisting of platinum nanoparticles on a ZIF-8 support（Pt@ZIF-8） was synthesized in a straightforward one-step procedure,by adding a nanostructured platinum sol during the formation of ZIF-8 at room temperature.Pt@ZIF-8 was highly porous and well crystallized.The Pt nanoparticles were well dispersed within the ZIF-8 support.In the hydrogenation of 1,4-butynediol,Pt@ZIF-8 exhibited high activity,excellent selectivity for 1,4-butenediol of greater than 94%,and reusability.The Pt@ZIF-8 catalyst did not require further additives.The favorable catalytic performance was attributed primarily to the modification of the ZIF-8 support by the platinum nanoparticles.

Multi-objective Evolutionary Algorithms for MILP and MINLP in Process Synthesis

Steady-state non-dominated sorting genetic algorithm (SNSGA), a new form of multi-objective genetic algorithm, is implemented by combining the steady-state idea in steady-state genetic algorithms (SSGA) and the fitness assignment strategy of non-dominated sorting genetic algorithm (NSGA). The fitness assignment strategy is improved and a new self-adjustment scheme of is proposed. This algorithm is proved to be very efficient both computationally and in terms of the quality of the Pareto fronts produced with five test problems including GA difficult problem and GA deceptive one. Finally, SNSGA is introduced to solve multi-objective mixed integer linear programming (MILP) and mixed integer non-linear programming (MINLP) problems in process synthesis.

Recent developments in selective laser processes for wearable devices

Recently,the increasing interest in wearable technology for personal healthcare and smart virtual/augmented reality applications has led to the development of facile fabrication methods.Lasers have long been used to develop original solutions to such challenging technological problems due to their remote,sterile,rapid,and site-selective processing of materials.In this review,recent developments in relevant laser processes are summarized under two separate categories.First,transformative approaches,such as for laser-induced graphene,are introduced.In addition to design optimization and the alteration of a native substrate,the latest advances under a transformative approach now enable more complex material compositions and multilayer device configurations through the simultaneous transformation of heterogeneous precursors,or the sequential addition of functional layers coupled with other electronic elements.In addition,the more conventional laser techniques,such as ablation,sintering,and synthesis,can still be used to enhance the functionality of an entire system through the expansion of applicable materials and the adoption of new mechanisms.Later,various wearable device components developed through the corresponding laser processes are discussed,with an emphasis on chemical/physical sensors and energy devices.In addition,special attention is given to applications that use multiple laser sources or processes,which lay the foundation for the all-laser fabrication of wearable devices.

Continuous,efficient and safe synthesis of 1-oxa-2-azaspiro[2.5]octane in a microreaction system

1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly acidic or basic byproducts,leading to considerable interest in the development of organic synthetic methods.Currently,the economically feasible route of production of 1-oxa-2-azaspiro[2.5]octane is the reaction of cyclohexanone with ammonia and sodium hypochlorite.However,due to strong exothermic reactions,massive gas release and heterogeneous reaction,the controllability,efficiency and safety of the reaction are in great difficulty using batch technology.In this paper,a microreaction system containing predispersion,reaction and phase separation was introduced into the preparation of 1-oxa-2-azaspiro[2.5]octane.The research results showed that precise control of the process including droplet dispersion,temperature control,reaction time control and fast continuous phase separation,was the key to process intensification.Under optimal conditions,the concentration of 1-oxa-2-azaspiro[2.5]octane in product obtained by microreaciton system(~2.0 mol·L^(-1))was much higher than that obtained by batch technology(0.2-0.4 mol·L^(-1)),which demonstrated that the continuous-flow synthesis would be a more efficient substitute for batch synthesis.Meanwhile,the results of the derivation experiments also showed that the aminating agent solution with higher concentration was more advantageous in the applications.

One-step Synthesis of ε-Caprolactam by the Liquid Phase Nitrosation of Cyclohexane over the Catalysts Containing CH_3COO^- or —COOH

ε-Caprolactam（CL or CPL） is one of the most important intermediates used in polymer industry for the production of several million tons of nylon-6 every year^[1]. All current commercial processes for the production of caprolactam are based on either benzene or tolueneI21. Caprolactam is synthesized by the Beckmann rearrangement of cyclohexanone oxime with fuming sulfuric acid or sulfuric acid as the reaction medium, and cyclohexanone oxime is produced by the reaction between cyclohexanone and hydro- xylamine（only one exception is the Toray PNC process）.

Fabrication of Al_2O_3-NaCl Composite Heat Storage Materials by One-step Synthesis Method

Thermal energy storage is an attractive option for effectiveness since it gives flexibility and reduces energy consumption and costs. New composite materials for storage and transformation of heat of NaCl-Al2O3composite materials were synthesized by one-step synthesis method. The chemical composition, morphology, structure, and thermal properties were investigated by XRD, EDS, SEM, and DSC. The results show that NaCl can be absorbed by Al2O3particle from 800 to 900 ℃ for Al2O3particle surface is rich active structure. The results also indicate that the leakage of NaCl when the phase change can be prevented by Al2O3particles and the enthalpy of phase change of NaCl-Al2O3material is 362 J/g. The composites have an excellent heat storage capacity. Therefore, this study contributes to one new thought and method to prepare high temperature heat storage material and this material can be applied in future thermal engineering.

An Integrated Process of a Two-Stage Fixed Bed Syngas Production and F-T Synthesis for GTL in Remote Gas Field

A novel process for catalytic oxidation of methane to synthesis gas (syngas), which consists of two consecutive fixed-bed reactors with air introduced into the reactors, integrated Fischer-Tropsch synthesis, was investigated. At the same time, a catalytic combustion technology has been investigated for utilizing the F-T offgas to generate heat or power energy. The results show that the two-stage fixed reactor process keep away from explosion of CH4/O2. The integrated process is fitted to produce diesel oil and lubricating oil in remote gas field.

A FUZZY MATCH BASED EXPERT SYSTEM FOR SYNTHESIS OF SEPARATION PROCESSES

A predictive parallel search algorithm,the fuzzy match inference strategy,is implemented ina prototype expert system.Selection of separation technologies and sequencing of separators are beingapproached in an integrated manner.The fuzzy match mechanism results in a relatively smaller subsetof favored schemes,constituting a hyperstructure for further quantitative evaluation and combinationoptimization.An industrial application example of aromatics extraction separation is presented.

Effects of Processing Conditions on Hydrothermal Synthesis of K_(0.5)Bi_(0.5)TiO_3 Nano-Powders

Potassium bismuth titanate nanosized powders were prepared by the hydrothermal method using Ti(C_4H_9O)_4 and Bi(NO_3)_3·5H_2O as raw materials in alkaline solution.The phase composition,particle size and morphology of the powders were studied by XRD and TEM analysis.The results showed that the powders were well crystallized and dispersed.The crystal phase of the powders was K_(0.5)Bi_(0.5)TiO_3 with the grain size of about 50 nm～100 nm.Hydrothermal temperature and alkaline concentrations had great effects on the phase composition and morphology of the resultant powders.Pure K_(0.5)Bi_(0.5)TiO_3 powders could be synthesized at 170℃～180℃with KOH concentration of 8 mol/L～12 mol/L.

Facile and Controlled Synthesis of Silica Sol Nanospheres Through a Modifi ed Sol-Gel Process

An effective and reproducible preparation of silica sol nanospheres via a modified sol-gel process has been described. Monodisperse and stable silica sol nanospheres with uniformsize were successfully obtained through the optimized synthesis in which the mixture of tetraethyl orthosilicate （TEOS） and ethanol was followed by the addition of water and ammonium hydroxide （NH3） separately, and the size of silica sol spheres was strictly controlled in the range of 25-119 nm with a narrow size distribution by fine adjustment of several reaction parameters. Results showed that in the presence of low concentration of TEOS, spheres size rose first and reached maximum when H2O concentration was up to 66 g/L. However, the diameter of silica sol spheres decreased above 66 g/L of H2O concentration. Furthermore, it was also found that the size and size distribution of silica sol nanospheres were affected by NH3 concentration. As NH3 concentration increased from 15 to 35 g/L, the diameter declined from 83 to 64 nm. Nevertheless, higher NH3 concentration would result in relatively broad size distribution, and gelation occurred when NH3 concentration reached 44 g/L. In addition, the effect of the different feed rates ofNH3 on the size growth of silica sol nanospheres was also discussed.

The Process of TiB_2-Cu Composite Phase and Structure Formation during Combustion Synthesis

The reaction process of combustion synthesis for TiB2 -Cu was investigated in detail using combustion-wave arresting experiment, X-ray diffraction （ XRD ） analysis, SEM analysis and differential thermal analysis （ DTA ）. The XRD analysis results for the different parts of the quenched specimen show that TiCux intermetallic phase firstly forms with the propagation of combustion wave, and then Ti1.87 B50 and Ti3B4 metastable phases come forth due to the diffusion of B atoms and finally the stable TiB2 phase forms because of the continuous diffusion of B atoms. The formation of TiB2 phase is uot completed by one step, but undergoes several transient processes. The process of reaction synthesis for Ti-B-Cu ternary system can be divided into three main stages： melting of Cu and Ti , and the formation of Cu- Ti melt and few TiCux , TiBx intermetallic phases ; large numbers of TiCux intermetallic phases formation and some fine TiB2 particles precipitation ; and the TiB2 particles coarsening and the stable TiB2 and Cu two phases formation in the final product.

Synthesis and Characterization of Triangular-pyramidal Bismuth Oxide via a One-step Chemical Precipitation Route

Triangular-pyramidal ω-Bi2O3 is successfully synthesized via a one-step wet-chemical method.XRD,SEM,and UV-vis have been employed to characterize the as-prepared samples.Structural characterization by XRD confirms the formation of triclinic ω-Bi2O3 with high purity.The well-defined flowerlike Bi2O3 structures consisted of many triangular-pyramids are formed.Preparative parameters,such as concentration of PEG 6000,have great effects on the morphology and the particle size.The obvious absorption edge for ω-Bi2O3 powder is located at about 493 nm,which corresponds to the optical band gap energy of2.73 eV.

A LOW-PRESSURE AND ONE-STEP METHOD FOR THE SYNTHESIS OF ALKYLIDYNETRICOBALT NONACARBONYL CLUSTERS:RCCo_8(CO)_9

Metal clusters RCCo_3(CO)_9(R-H,C1,Br,CH_3,Ph) were prepared in 18.8-57.3% yields from the reaction of cobalt(Ⅱ)salt and RCX_a under mild PTC conditions(latm CO,25℃).The cobalt salt was reduced to Co(CO)_4 in the presence of Na_3S_2O_4.

Scale-Up of the Polyol Process for Nanomaterial Synthesis

Two classes of inorganic materials such as metallic nanowires and metal oxides nanorods were synthesized using the polyol process and scaled-up to produce macroscopic quantities. Scale-up strategy was successfully built by performing the synthesis in a 15 cm diameter, 4.5 litersvolume cylindrical tank using a straight paddle impeller and a Rushton turbine. The actual yield of the synthesis is ~45 grams per batch for zinc oxide nanorods and ~20 grams per batch for cobalt nickel nanowires. Under the same rotation speed, the aspect ratio of the produced nanowires and nanorods using the Rushton turbine impeller with radial flow patterns has shown a lower aspect ratio, nanoparticle size and polydispersity. This is attributed to the increase of the local dissipated energy as spatially calculated by computational fluid dynamics (CFD) that is proposed to design, optimize and scale-up the polyol process.