Effect of Solvent on Nanoparticle Production of β‐Carotene by a Supercritical Antisolvent Process

Production of micro‐ to nano‐sized particles of β‐carotene was investigated by means of solution‐enhanced dispersion by supercritical fluids (SEDS). β‐Carotene was dissolved in dichloromethane (DCM), N,N‐dimethylformamide (DMF), n‐hexane, or ethyl acetate, and supercritical CO₂ served as an antisolvent. The effects of the organic solvents, operating pressure, and temperature were examined. The morphologies of the particles produced by the SEDS were observed by field emission‐scanning electron microscopy and particle sizes were determined by image analysis. Irregularly shaped microparticles were produced in the system with DCM and DMF solution. Plate‐like microparticles were generated by using n‐hexane solution and irregular nanoparticles by ethyl acetate solution. The optimum operating conditions were found to be ethyl acetate as solvent in a defined pressure and temperature range.     

Encapsulation of Lavandin Essential Oil in Poly‐(ϵ‐caprolactones) by PGSS Process

Lavandin essential oil has been encapsulated in poly‐(?‐caprolactone) (MW: 4000 g mol^–1) by means of the particles from gas saturated solutions (PGSS) process. The influence of process conditions, i.e., pre‐expansion temperature and pressure, and oil/polymer mass ratio, on the morphology of particles and the efficiency of encapsulation has been analyzed. Spherical particles with particle sizes of 100–700 μm were obtained, with increasing particle sizes and more agglomeration as the oil/polymer ratio was increased. The efficiency of encapsulation was increased by conditions that favored a fast solidification of the polymer shell, including high pre‐expansion pressures, reaching efficiencies up to 50 % with oil loads up to 120 mg oil/g particles.     

Non‐Isothermal Kinetic Study of the Thermal Decomposition of Melamine 3‐Nitro‐1,2,4‐triazol‐5‐one Salt

Study on thermal behavior of 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) salts was required to obtain important data for application purposes. These compounds have been shown to be useful intermediates for gun propellant ingredients, high energetic ballistic modifiers for solid propellants and other potential applications. In this paper, thermal decomposition and non‐isothermal kinetics of melamine 3‐nitro‐1,2,4‐triazol‐5‐one salt (MNTO) were studied under non‐isothermal conditions by DSC and TG methods. The kinetic parameters were obtained from analysis of the DSC and TG curves by Kissinger and Ozawa methods. The critical temperature of thermal explosion (T_b) was 574 K. The results show that MNTO is thermally more stable than NTO when compared in terms of the critical temperature of thermal explosion. Finally, the values of ΔS^#, ΔH^#, and ΔG^# of its decomposition reaction were calculated.     

Indirect Synthesis of Bis(2‐PhInd)ZrCl2 Metallocene Catalyst,Kinetic Study and Modeling of Ethylene Polymerization

Bis(2‐phenylindenyl)zirconium dichloride (bis(2‐PhInd)ZrCl₂) catalyst was synthesized via the preparation of bis(2‐phenylindenyl)zirconium dimethyl (bis(2‐PhInd)ZrMe₂) followed by chlorination to obtain the catalyst. Performance of the catalyst for ethylene polymerization and its kinetic behavior were investigated. Activity of the catalyst increased as the [Al]:[Zr] molar ratio increased to 2333:1, followed by reduction at higher ratios. The maximum activity of the catalyst was obtained at a polymerization temperature of 60 °C. The rate‐time profile of the reaction was of a decay type under all conditions. A general kinetic scheme was modified by considering a reversible reaction of latent site formation, and used to predict dynamic polymerization rate and viscosity average molecular weight of the resulting polymer. Kinetic constants were estimated by the Nelder‐Mead numerical optimization algorithm. It was shown that any deviation from the general kinetic behavior can be captured by the addition of the reversible reaction of latent site formation. Simulation results were in satisfactory agreement with experimental data.     

Green Medium for the Hydrolysis of 5‐Cyanovaleramide

Hydrolysis of 5‐cyanovaleramide (5‐CVAM) in near‐critical water without the addition of any catalyst has been demonstrated. The results demonstrated that the cyano group at one end of the carbon of 5‐CVAM is more reactive than the amide group at the other end, under the same experimental conditions. The relations between 5‐CVAM concentration and residence time revealed that hydrolysis of 5‐CVAM shows second‐order reaction kinetics in the investigated temperature range. The rate constants, average apparent activation energy and pre‐exponential factor were evaluated according to the Arrhenius equation. Based on the experimental results, a carbon balance was calculated, and a hydrolysis reaction scheme of 5‐CVAM was proposed.     

Modeling of Kinetic Expressions for the Reduction of NOx by Hydrogen in Oxygen‐Rich Exhausts Using a Gradient‐Free Loop Reactor

The reduction of NO_x by hydrogen under lean conditions is investigated in a gradient‐free loop reactor. Using this computer‐controlled reactor, the reaction rates can be measured under exact isothermal conditions. Systematic variation of the input concentrations of hydrogen, nitric oxide, oxygen as well as reaction temperature provides a complete data set of reaction rates for the given reaction system. A number of kinetic rate expressions were evaluated for their ability to fit the experimental data by using toolboxes of MATLAB. The temperature influence on reaction rate constants and adsorption equilibrium constants were correlated simultaneously using Arrhenius and van’t Hoff equations, respectively. The kinetic rate expression based on a Langmuir‐Hinshelwood‐type model describes the data and the model can be improved by introducing a correction term in square root of hydrogen partial pressure over the range of conditions investigated.     

Fischer‐Tropsch Synthesis Over Co‐Ru/γ‐Al2O3 Catalyst in Supercritical Media

The Fischer‐Tropsch synthesis (FTS) in gaseous and supercritical phases was examined in a continuous, high‐pressure fixed‐bed reactor by employing a cobalt catalyst (Co‐Ru/γ‐Al₂O₃). The kinetic modeling of the FTS was investigated in the reactor over a 60–80 mesh cobalt catalyst. The Langmuir‐Hinshelwood kinetic equation was used for both the Fisher‐Tropsch (FT) and water gas shift (WGS) reactions. The kinetic model was applied for simulation of the reactor with 16–20 mesh cobalt catalyst. The simulation results showed a good agreement with the experimental data. The experimental data showed that higher CO conversion and lower CH₄ and CO₂ selectivities were achieved in supercritical media compared to the gaseous phase. The BET surface area and pore volume enhancement results provided evidence of the higher in situ extraction and greater solubility of heavy hydrocarbons in supercritical media than in gaseous phases. Furthermore, the effects of supercritical solvent such as n‐pentane, n‐hexane, n‐heptane and their mixtures were studied. Moreover, the influence of reaction temperature, H₂/CO ratio, W/F_(CO+H2) and pressure tuning in the supercritical media FT synthesis were investigated, as well as the effect of the supercritical fluid on the heat transfer within the reactor. The product carbon distribution had a similar shape for all types of solvents and shifted to lighter molar mass compounds with increasing temperature, H₂/CO ratio, and W/F_(CO+H2). Finally, the product distribution shifted to higher molar mass hydrocarbons with increasing pressure. As a result, one may conclude that a mixture of hydrocarbon products of the FTS can be used as a solvent for supercritical media in Fischer‐Tropsch synthesis.     

Reduced Kinetic Mechanism of n‐Heptane Oxidation in Modeling Polycyclic Aromatic Hydrocarbon Formation in Diesel Combustion

A reduced chemical mechanism was developed for the chemical kinetics of n‐heptane oxidation in modeling polycyclic aromatic hydrocarbon formation in diesel combustion. The complete kinetic mechanism, which comprises five hundred and seventy‐two reactions and one hundred and eight species, was reduced to a minor mechanism that includes only seventy‐six reactions and forty‐eight species by using net reaction rate analysis and sensitivity analysis, yet the model based on this reduced mechanism predicted the temperature profile and concentrations of C₇H₁₆, O₂, H₂O, CO₂, benzene, naphthalene, phenanthrene, biphenyl, and pyrene that are essentially indistinguishable from those of the complete mechanism under the range of reaction conditions of interest.     

Kinetic and Technological Analysis of Dimethyl Toluene‐2,4‐Dicarbamate Synthesis

The synthesis of dimethyl toluene‐2,4‐dicarbamate from 2,4‐toluene diamine and dimethyl carbonate is a complex reaction system. First, the reaction enthalpies, the Gibbs function changes, and the equilibrium constants of the reactions were calculated by several methods of group contribution. Secondly, the kinetics of the synthesis reaction over a zinc acetate catalyst was investigated in a batch autoclave. The kinetic model equations were established by parameter estimation based on experimental data, and the model met the requirements of the statistical test. The calculated results based on the model agreed well with the experimental data. According to the results of both thermodynamic calculation and kinetic analysis, the influence of some technological parameters, such as content of methanol in the feed and reaction temperature, on the synthesis reaction was discussed.     

Termolecular Kinetic Model for CO2‐Alkanolamine Reactions: An Overview

The CO₂ reaction with alkanolamines has received considerable attention by both academia and industry. Commonly, the formation of the carbamate during the CO₂ reaction with primary, secondary, and sterically hindered amines is described by a two‐step zwitterion mechanism. Alternatively, a single‐step termolecular reaction mechanism can also be used to govern carbamate formation. The experimental kinetic data for several amine‐based solvents are consistent with this mechanism, and it can satisfactorily explain fractional‐order and higher‐order kinetics. However, up to now, the termolecular reaction mechanism has not been properly discussed. Here, this mechanism is described in detail, a simple procedure to estimate the kinetic parameters is outlined, and the termolecular reaction kinetics for various systems comprising individual and mixed amines is reviewed.     

Supercritical antisolvent micronisation of synthetic all‐trans‐β‐carotene with tetrahydrofuran as solvent and carbon dioxide as antisolvent

BACKGROUND: Supercritical antisolvent (SAS) micronisation of synthetic trans ‐β‐carotene was studied using tetrahydrofuran (THF) as solvent and supercritical carbon dioxide (CO₂) as antisolvent, with the objective of increasing its bioavailability and facilitating its dispersion in oil and emulsion formulations as a result of its smaller particle size. The micronised powder was analysed by scanning electron microscopy and high‐performance liquid chromatography. Micronisation experiments were performed in order to evaluate the effects of temperature (308.15–333.15 K), pressure (6.5–13 MPa) and concentration of the liquid solution (6–9 g L^?1). The effect of the supercritical CO₂/THF flow ratio in the range between 4 and 44 (on a mass basis) was also analysed. Determinations of equilibrium concentrations of β‐carotene in the CO₂/THF mixture were also performed. RESULTS: The particle size obtained ranged from 1 to 500 µm, with mean particle diameters around 100 µm. Three types of morphology were found in the precipitated powder: crystalline with superficial pores and leaf‐like appearance; crystalline with regular shapes and blade‐like edges; and crystalline without superficial pores and leaf‐like apearance. The Peng–Robinson equation of state was used to calculate the density of the CO₂/THF binary mixture, and the solubility of β‐carotene in this mixture was correlated with its density. CONCLUSION: The use of the SAS technique to micronise β‐carotene proved to be efficient, and the absence of degradation in the micronised powder allows the industrial application of this technique. Copyright © 2008 Society of Chemical Industry     

Modeling of Gas‐Solid Reactions: Kinetics,Mass and Heat Transfer,and Evolution of the Pore Structure

Mathematical models for simulating heterogeneous gas‐solid reactions must describe a complex set of physicochemical and thermal phenomena. These include the chemical reaction itself, at an interface whose area varies during the conversion, the transport of gaseous species by diffusion in the pores of the solid, whose size and number generally change in the course of reaction, diffusional transport in the layer of solid product, the evolution or consumption of heat by the reaction and its transport in the porous solid, etc. The present paper gives details of the equations employed to model each of these processes. Some computed results illustrate how increasingly sophisticated recent models describe the gradual obstruction of pores during reactions, such as the sulfation of lime, or the thermal effects related to the exothermic nature of the oxidation of zinc sulfide.     

Synthesis Gas Production Configurations for Gas‐to‐Liquid Applications

Different syngas configurations in a gas‐to‐liquid plant are studied including autothermal reformer (ATR), combined reformer, and series arrangement of gas‐heated reformer and ATR. The Fischer‐Tropsch (FT) reactor is based on a cobalt catalyst and the degrees of freedom are steam‐to‐carbon ratio, purge ratio of light ends, amount of tail gas recycled to synthesis gas (syngas) and FT synthesis units, and reactor volume. The production rate of liquid hydrocarbons is maximized for each syngas configuration. Installing a steam methane reformer in front of an ATR will reduce the total oxygen consumption per barrel of product by 40 % compared to the process with only an ATR. The production rate of liquid hydrocarbons is increased by 25.3 % since the flow rate of the purge stream for the ATR is the highest one compared to other configurations and contains mainly CO₂.     

4,5‐Bis(5‐tetrazolyl)‐1,2,3‐triazole: Synthesis and Performance

4,5‐Bis(5‐tetrazolyl)‐1,2,3‐triazole (BTT) was synthesized by a new method. Its structure was characterized by IR and ¹³C NMR spectroscopy and elemental analysis (EA). The thermal stability of BTT was investigated by TG‐DSC technique. The kinetic parameters including activation energy and pro‐exponential factor were calculated by Kissinger equation. The combustion heat, detonation products, hygroscopicity, impact, and friction sensitivity were also measured. The formation heat, detonation pressure, and detonation velocity of BTT were calculated. BTT has high detonation pressure and detonation velocity (P=35.36 GPa, D=8.971 km s⁻¹). BTT has potential application prospect as environmentally friendly gas generant, insensitive explosive and solid propellant.     

A Zinc(II) Catalyst System for the Conia‐Ene Reaction of Alkynyl‐Aminomalonates Applicable to 5‐Endo‐Dig Reactions

The zinc(II)‐catalyzed 5‐exo‐dig (Conia‐ene) and 5‐endo‐dig cyclizations of a range of alkynyl‐α‐aminomalonates give rise to nitrogen heterocycles with good efficiency. The reaction allows the synthesis of a broad range of synthetically useful building blocks.     

5‐Fluorouracil encapsulated magnetic nanohydrogels for drug‐delivery applications

For the first time, green‐tea (GT)‐based magnetic nanohydrogels were developed for drug‐delivery purposes. The hydrogel matrices were fabricated via the in situ polymerization of acrylamide with GT molecules. Magnetic nanoparticles were synthesized by the reduction of the 1:2 molar ratio mixture of ferrous sulfate heptahydrate and ferric chloride hexahydrate with an ammonia solution. A chemotherapeutic drug, 5‐fluorouracil, was chosen as a model drug, and its releasing profiles in the presence and absence of the external magnetic field were evaluated at a pH of 7.4. We observed that in the presence of the applied magnetic field, these magnetic nanohydrogels released 2.86% more drug than in the absence of a magnetic field. The magnetic nanohydrogels were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, vibrating sample magnetometry, and transmission electron microscopy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43921.     

DFT and MP2 Study of Intermolecular Interaction of 5‐Aminotetrazole and Hydrazine: Enthalpy of Formation of Hydrazinium 5‐Aminotetrazolate in the Gas Phase

The tautomerism of all possible forms of 5‐aminotetrazole ( AT1 – AT7 ) in the gas phase and continuum solvent was studied theoretically. The calculations were separately performed at the MP2 and CAM‐B3LYP levels of theory, using the 6‐311++G(d,p) basis set. It was found that 5‐aminotetrazole in the 2H form ( AT1) is the most stable isomer in both the gas phase and in solution. In addition, the aggregation of various isomers of 5‐aminotetrazole with hydrazine was investigated in the gas phase and in solution. Finally, the standard enthalpy of formations of the different structures of hydrazinium 5‐aminotetrazolate was determined in the gas phase. Using the calculated standard enthalpy of formation of different structures of hydrazinium 5‐aminotetrazolate in the gas phase and considering their Boltzmann population ratios, a single value has been reported for the standard enthalpy of formation of hydrazinium 5‐aminotetrazolate considering all of the tautomers. The calculated values are in excellent agreement with the experimentally reported heat of formation for the hydrazinium 5‐aminotetrazolate.     

Synthesis of functionalizable and biodegradable polymers via ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate and ε‐caprolactone

The biomedical applications of poly(ε‐caprolactone) (PCL) were limited for its high hydrophobicity and crystallinity. In this study, we copolymerized CL with amorphous 5‐hydroxyl‐trimethylene carbonate (HTMC) to solve the problem. The 5‐benzyloxy‐trimethylene carbonate (BTMC) was synthesized to copolymerize with CL, then hydrogenolyzed to obtain hydroxyl pendant groups. A serial of copolymers with different BTMC molar ratio were synthesized and their chemical structures and thermal properties were thoroughly studied with NMR, FT‐IR, GPC, XRD, DSC, and TGA. Finally we examined the water contact angle of the copolymers. DSC and XRD results showed that the PCL segments in the copolymers crystallized below 16.8%. BTMC molar content and the crystallinity of the copolymers increased after hydrolysis. With the introduced hydroxyl pendant groups, the deprotected copolymers improved their hydrophilic property significantly, and the copolymer with 9.3% HTMC molar content had static water contact angle as low as 36.5°. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Reactor Modeling of Gas‐Phase Polymerization of Ethylene

A model is developed for evaluating the performance of industrial‐scale gas‐phase polyethylene production reactors. This model is able to predict the properties of the produced polymer for both linear low‐density and high‐density polyethylene grades. A pseudo‐homogeneous state was assumed in the fluidized bed reactor based on negligible heat and mass transfer resistances between the bubble and emulsion phases. The nonideal flow pattern in the fluidized bed reactor was described by the tanks‐in‐series model based on the information obtained in the literature. The kinetic model used in this work allows to predict the properties of the produced polymer. The presented model was compared with the actual data in terms of melt index and density and it was shown that there is a good agreement between the actual and calculated properties of the polymer. New correlations were developed to predict the melt index and density of polyethylene based on the operating conditions of the reactor and composition of the reactants in feed.     

Improved Synthesis and X‐Ray Structure of 5‐Aminotetrazolium Nitrate

5‐Aminotetrazolium nitrate was synthesized in high yield and characterized using Raman and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N). The molecular structure of 5‐aminotetrazolium nitrate in the crystalline state was determined by X‐ray crystallography: monoclinic, P 2₁/c, a=1.05493(8) nm, b=0.34556(4) nm, c=1.4606(1) nm, β=90.548(9)°, V=0.53244(8) nm³, Z=4, ϱ=1.847 g cm⁻³, R₁=0.034, wR₂ (all data)=0.090. The thermal stability of 5‐aminotetrazolium nitrate was determined using differential scanning calorimetry; the compound decomposes at 167 °C. The enthalpy of combustion (Δ_combH) of 5‐aminotetrazolium nitrate ([CH₄N₅]⁺[NO₃]⁻) was determined experimentally using oxygen bomb calorimetry: Δ_combH([CH₄N₅]⁺[NO₃]⁻)=−6020±200 kJ kg⁻¹. The standard enthalpy of formation (Δ_fH°) of [CH₄N₅]⁺[NO₃]⁻ was obtained on the basis of quantum chemical computations at the electron‐correlated ab initio MP2 (second order Møller‐Plesset perturbation theory) level of theory using a correlation consistent double‐zeta basis set (cc‐pVTZ): Δ_fH°([CH₄N₅]⁺[NO₃]⁻(s))=+87 kJ mol⁻¹=+586 kJ kg⁻¹. The detonation velocity (D) and the detonation pressure (P) of 5‐aminotetrazolium nitrate were calculated using the empirical equations by Kamlet and Jacobs: D([CH₄N₅]⁺[NO₃]⁻)=8.90 mm μs⁻¹ and P([CH₄N₅]⁺[NO₃]⁻)=35.7 GPa.