Catalysis with Gas-Expanded Liquids: We have exploited the pressure-tunable properties of gas-expanded liquids (GXLs) in a variety of catalytic systems. At ambient temperatures, gases such as carbon dioxide (CO2) and light hydrocarbons (such as propylene and ethylene) are close to their critical temperatures. When mildly compressed (to tens of bars) at such temperatures, they dissolve in most conventional solvents and volumetrically expand them. The increased free volume of the GXL phases accommodates permanent gases such as O2, H2 and CO in unusually high concentrations. We have harnessed these unique properties to demonstrate several novel GXL-based catalytic reaction engineering concepts. These include (a) highly selective hydroformylations at mild conditions;(b) inherently safe ethylene epoxidation process that eliminates CO2 formation as a byproduct; (c) formation of high purity terephthalic acid with reduced solvent burning and carbon footprint; and (d) Facile CO2 electrochemistry in CO2-expanded electrolytes.

Chemical plants involving batch and semi-continuous processes have become important of late, due to the production of high value products and/or low production quantities (for example, pharmaceutical manufacturing). Batch processes are characterized by the use of general purpose equipment for multiple tasks and therefore, scheduling is vital in the design process. Design, scheduling and selection of an operating strategy must therefore be considered as a single integral problem. A single monolithic mathematical programming formulation for design and scheduling would result in a problem too large to solve using existing computational tools. The proposed approach decomposes the problem into the planning and scheduling stages. The planning and scheduling stages are posed as mixed integer linear programs (MILP). The planning stages consists of aggregate resource constraints which act as surrogate scheduling constraints. The uncertainty in demand and value of products is incorporated in the planning problem through discrete scenarios. First, the aggregate problem is solved for the design solution. The operability (and feasibility) of this design is tested by solving a series of scheduling problems implied by the design solution. A set of heuristics act as feedback to the planning stage if any of the scheduling problems are infeasible. Utilizing the monolithic design-scheduling model, the planning problem is derived and a theoretical relationship established between the aggregate problem and the monolithic model. A hierarchy of aggregate problems is derived, based on which an algorithm is developed to obtain optimal solutions to the overall design problem. The computation efficiency is greatly enhanced through the implementation of a sophisticated distributed algorithm to exploit the parallel structure exhibited by the design and scheduling MILPs. The methodology is validated through a large industrial case study and extended by applying it to other problems in the processing industry (waste treatment options integrated with design, supply chain management, strategic business planning).


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Hydrogels are frequently used in tissue engineering and regenerative medicine, drug delivery, and environmental remediation. Alginate and gelatin, which are frequently used natural polymers to form hydrogels, were chosen in this study to form a core-shell structured hydrogel. Cryogels and aerogels were obtained by drying hydrogels with different methods, freeze-drying, and the continuous flow of supercritical CO2, respectively. The potential use of hydrogels, aerogels, and cryogels as a tissue scaffold was evaluated comparatively. Characterizations of materials were determined morphologically by scanning electron microscope and computed-micro tomography, chemically by energy dispersive spectroscopy, and mechanically by the dynamic mechanical analyzer. In addition, the cytotoxic effect of all structures was analyzed by the WST-1 method and the localization of the cells in these structures was determined by microscopic methods. All scaffolds show non-cytotoxic effects. Cryogels have the highest porosity (85.21 %) and mean pore size values (62.326.8 m). Additionally, cryogels show high water retention capacity (78253.5%) than aerogels (3892.5%) for 24 h. The elastic modulus values were be457b7860

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