Experimental,equilibrium modelling,and column design for the reactive separation of biomass-derived 2-furoic acid

Electrochemical conversion of biomass to value-added chemicals has gained impetus in recent years. Herein, we present a methodology for recovering biomass-derived 2-furoic acid from the dilute aqueous stream by reactive extraction. The reactive extraction was performed using a chemical extractant, trioctylamine (TOA), with diluents (octanol, chloroform, and diethyl ether). Equilibrium parameters influencing the recovery of 2-furoic acid were evaluated. Using TOA in various diluents, the 2-furoic acid was recovered with 85%–99% efficiency. A 1:1 complex of the 2-furoic acid—TOA was formed in the organic phase, and the experimental equilibrium complexation constant was compared with that obtained from the relative basicity and Langmuir models. The equilibrium parameters were used for column design to estimate the solvent to feed ratio (S/F) and the number of theoretical stages (NTS). The NTS required is 12 to attain 99% recovery of 2-furoic acid in counter-current extraction. The present study sheds light on the reactive extraction process adopted for process intensification with electrochemical conversion, paving the way for the commercialization of valuable products obtained from biomass.     

Deep learning-based hybrid reconstruction algorithm for fibre instance segmentation from 3D x-ray tomographic images

3D x-ray tomography is a powerful scanning technique used for generating images of complex fibre structures. A novel machine-learning algorithm to identify and separate individual fibres using 3D images is proposed in this article. The developed four-step hybrid 3D fibre segmentation algorithm involves deep-learning aided semantic segmentation that slices 3D images to create 2D images for fibre extraction, elliptical contour estimation combined with the marker-controlled watershed algorithm for separating fibres from the background area, identifying individual fibres through 3D reconstruction, and, lastly, the 3D object refining approach based on outlier object detection and replacement. The proposed methodology is implemented on a real-time sample of nylon fibre bundle under compression and its 3D x-ray image volume to validate the performance. The results show its superior performance compared to off-the-shelf image processing algorithms in terms of precision, that is, with a validation accuracy greater than 90%, and efficiency, that is, preventing the need for a huge data set and reducing the complexity.     

Performance of clay masonry prisms with light weight plaster exposed to standard fire exposure

Clay bricks are one of the most widely used materials in building construction due to their advantages, including local availability, ease of fabrication and cost-effectiveness. Fire is one of the dangerous hazards that can cause damage the life and property. Lightweight plasters play a vital role in insulating the masonry construction during fire accident. There is only limited data and information available on the fire performance of Clay Brick Masonry (CBM) insulated with lightweight plaster. An extensive investigation was undertaken to evaluate the residual strength properties and physical characteristics of CBM prisms exposed to elevated temperatures. CBM prisms plastered with M-sand mortar, vermiculite mortar, and perlite mortar were used for the investigation. Protected prisms were exposed to elevated temperatures following the ISO 834 standard fire curve for durations of 30 min (821°C), 60 min (925°C), 90 min (986°C), and 120 min (1029°C). Mechanical properties such as axial load carrying capacity, stress–strain behaviour, elastic modulus, and crack pattern were examined. The mechanical properties of CBM prisms were found to be highly influenced by the type of plastering, intensity, and the duration of heating. The microstructure and image analysis confirmed the effects of temperature exposure on protective plasters. Equations are proposed to determine the residual axial compressive strength and the elastic modulus of CBM. It was found that the specimens plastered with perlite mortar had better fire resistance.     

Vapor Phase Beckmann Rearrangement of Cyclohexanone Oxime over Different Ferrierite Zeolite Catalysts

Ferrierite zeolite catalysts prepared using different procedures have been tested for their activity for vapor phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam. We report here the results of a study seeking the influence of temperature, nitrogen feed rate, oxime concentration and solvents on the catalyst performance. At low concentration of oxime (2.5 wt%), using acetonitrile as solvent the maximum in the conversion of oxime and selectivity to -caprolactam has been obtained. The presence of weak, medium and strong acid sites as indicated by temperature-programmed desorption of NH₃ corroborates well with the catalytic activities of various ferrierites shown here. Solvent polarity is found to significantly affect the conversion of cyclohexanone oxime.     

Proteomics analysis of carbon-starved Mycobacterium smegmatis: induction of Dps-like protein

Mycobacterium tuberculosis is a globally successful pathogen,infecting more than one third of total world's population. Thesebacteria have the remarkable ability to persist in the hostfor long periods of time unrecognized by the immune system andthen to re-emerge later in life causing the disease. The physiologyof such persistent or dormant bacilli is not very well characterized.Some evidence suggests that the dormant bacilli survive in anutrient-deprived state that is similar to the stationary phaseof the bacteria with respect to gene expression and physiology.Under this assumption we have studied the survival of Mycobacteriumsmegmatis in carbon starvation conditions as a model for mycobacterialpersistence. M.smegmatis, being a fast-growing strain, servesas a good model to study starvation responses. Using the two-dimensionalelectrophoresis-based proteomics approach, we identified a proteinwhich was found to be expressed preferentially under starvationconditions. This protein is homologous to a family of proteinscalled Dps (DNA binding Protein from Starved cells) that areknown to protect DNA under various kinds of environmental stressesand its existence has, so far, not been reported in mycobacteria.Upon expression and purification of this protein, we observedthat it has non-specific DNA-binding ability. Formation of acage-like dodecamer structure is a characteristic feature ofDps. Using comparative modelling we were able to show that Dpsfrom M.smegmatis could form a dodecamer structure similar tothe crystal structure of Dps from Escherichia coli.     

Design and assessment of delay timer alarm systems for nonlinear chemical processes

In process and manufacturing industries, alarm systems play a critical role in ensuring safe and efficient operations. The objective of a standard industrial alarm system is to detect undesirable deviations in process variables as soon as they occur. Fault detection and diagnosis systems often need to be alerted by an industrial alarm system; however, poorly designed alarms often lead to alarm flooding and other undesirable events. In this article, we consider the problem of industrial alarm design for processes represented by stochastic nonlinear time‐series models. The alarm design for such complex processes faces three important challenges: (1) industrial processes exhibit highly nonlinear behavior; (2) state variables are not precisely known (modeling error); and (3) process signals are not necessarily Gaussian, stationary or uncorrelated. In this article, a procedure for designing a delay timer alarm configuration is proposed for the process states. The proposed design is based on minimization of the rate of false and missed alarm rates—two common performance measures for alarm systems. To ensure the alarm design is robust to any non‐stationary process behavior, an expected‐case and a worst‐case alarm designs are proposed. Finally, the efficacy of the proposed alarm design is illustrated on a non‐stationary chemical reactor problem. © 2017 American Institute of Chemical Engineers AIChE J, 63: 77–90, 2018     

Reversible,repeatable and low phase transition behaviour of spin coated nanostructured vanadium oxide thin films with superior mechanical properties

Smooth, uniform and crystalline vanadium oxide thin films were deposited on quartz by spin coating technique with four different rpm i.e., 1000, 2000, 3000 and 4000 and subsequently post annealed at 350, 450 and 550?°C in vacuum. Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) techniques were utilized for microstructural characterizations and phase analysis, respectively, for vanadium oxide powder and deposited film. Nanorods were observed to be grown after vacuum annealing. X-ray photoelectron spectroscopy (XPS) technique was utilized to study the elemental oxidation state of deposited vanadium oxide films. Thermo-optical and electrical properties such as solar transmittance (τ_s), reflectance (ρ_s), absorptance (α_s), infrared (IR) emittance (ε_ir) and sheet resistance (R_s) of different thin films were evaluated. Based on the optical characteristics the optimized condition of the film processing was identified to be spin coated at 3000?rpm. Subsequently, the nanoindentation technique was utilized to measure hardness and Young's modulus of the optimized film. The measured nanomechanical properties were found to be superior to those reported for sputtered vanadium oxide films. Finally, temperature dependent phase transition characteristics of optimized vanadium oxide films were studied by differential scanning calorimetry (DSC) technique. Reversible and repeatable phase transition was found to occur in the range of 44–48?°C which was significantly lower than the phase transition temperature (i.e., 68?°C) of bulk VO₂.     

Waste Eggshell-Derived Calcium Oxide and Nanohydroxyapatite Biomaterials for the Preparation of LLDPE Polymer Nanocomposite and Their Thermomechanical Study

Waste eggshells were utilized to make calcium oxide (E-CaO) and hydroxyapatite (E-HAP). E-CaO obtained by heat treatment to eggshells was utilized for the synthesis of E-HAP. Melt compounding of E-CaO/E-HAP was performed with linear low-density polyethylene (LLDPE) on a Brabender Plastograph and ground the obtained formulation for injection molding. Addition of E-CaO/E-HAP in the LLDPE significantly enhanced the flame retardant ability and thermal stability of resultant composites. In the comparative study, E-HAP nanopowder-containing polymer composite showed increment in thermal and mechanical properties than the composite prepared using E-CaO.     

Studies on the copolymerization of methyl methacrylate with N‐(o/m/p‐chlorophenyl) itaconimides

The article describes the synthesis and characterization of N‐aryl itaconimide monomers such as: N‐(p‐chlorophenyl) itaconimide (PI)/N‐(m‐chlorophenyl) itaconimide (MI)/N‐(o‐chlorophenyl) itaconimide (OI) and its copolymerization behavior with MMA. The homopolymers and copolymers of N‐aryl itaconimides and methyl methacrylate (MMA, M₂) were synthesized by varying the mol fraction of N‐aryl itaconimides in the initial feed from 0.1 to 0.5 using azobisisobutyronitrile (AIBN) as an initiator and tetrahydrofuran (THF) as the solvent. Copolymer composition was determined using ¹H‐NMR spectroscopy [by taking the ratio of intensities of signals due to ? OCH₃ of MMA (δ = 3.59 ppm) and the aromatic proton (δ = 7.2–7.5 ppm) of N‐aryl itaconimides] and percent nitrogen content. The reactivity ratios were found to be r₁ = 1.33 and r₂ = 0.36 (PI‐MMA) r₁ = 1.15 and r₂ = 0.32 (MI‐MMA) and r₁ = 0.81 and r₂ = 0.35 (OI‐MMA). Molecular weight as determined using high‐performance liquid chromatography decreased with increasing mol fraction of itaconimides in copolymers. All the polymers had a polydisperstivity index in the range of 1.5–2.6.Thermal characterization was done using differential scanning calorimetry and dynamic thermogravimetry in nitrogen atmosphere. Incorporation of these N‐aryl itaconimides in PMMA backbone resulted in an improvement in glass transition temperature (T_g) and thermal stability. Percent char increased with the increase of PI/MI/OI content in the copolymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2078–2086, 2001