Experimental investigations and model-based optimization of CZZ/H-FER 20 bed composition for the direct synthesis of DME from CO2-rich syngas

Experimental kinetics studies and model-based optimization were performed for the direct synthesis of dimethyl ether (DME) in a wide range of process conditions, including various CuO/ZnO/ZrO2:H-FER 20 bed compositions. This,...

Structural Adaptive, Self-Separating Material for Removing Ibuprofen from Waters and Sewage

β-Cyclodextrin nanosponge (β−CD−M) was used for the adsorption of ibuprofen (IBU) from water and sewage. The obtained material was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET), Barrett–Joyner–Halenda (BJH), Harkins and Jura t-Plot, zeta potential, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and elementary analysis (EA). Batch adsorption experiments were employed to investigate the effects of the adsorbent dose, initial IBU concentration, contact time, electrolyte ions and humic acids, and sewage over adsorption efficiency. The experimental isotherms were show off using Langmuir, Freundlich, Hill, Halsey and Sips isotherm models and thermodynamic analysis. The fits of the results were estimated according to the Sips isotherm, with a maximum adsorption capacity of 86.21 mg g−1. The experimental kinetics were studied by pseudo-first-order, pseudo-second-order, Elovich, modified Freundlich, Weber Morris, Bangham’s pore diffusion, and liquid film diffusion models. The performed experiments revealed that the adsorption process fits perfectly to the pseudo-second-order model. The Elovich and Freundlich models indicate chemisorption, and the kinetic adsorption model itself is complex. The data obtained throughout the study prove that this nanosponge (NS) is extremely stable, self-separating, and adjusting to the guest structure. It also represents a potential biodegradable adsorbent for the removal IBU from wastewaters.

Modification of the Luedeking and Piret Model with a Delay Time Parameter for Biotechnological Lactic Acid Production

Objectives To obtain a mathematical model that adequately describes the time lag between biomass generation and lactic acid production of lactic fermentations. Methods Seven experimental kinetics from other research works were studied to validate our proposal: four studies of Fungal Submerged Fermentation and three cases of Bacterial Submerged Fermentation, including the data recollected by Luedeking and Piret. Results We introduce a modification to the Luedeking and Piret model that consist in the introduction of a time delay parameter in the model, this parameter would account for the lag time that exists between the production of biomass and lactic acid. It is possible to determine this time delay in a simple way by approximating the biomass and product formation considering that they behave as a first order plus dead time system. The duration of this phenomenon, which is not described with the classical Luedeking and Piret model, is a function of microorganism physiology (ease of biomass growth), environment (nutrients) and type of inoculum. Conclusion The Luedeking and Piret with delay model applications reveal an increase of the R2 in all cases, evidencing the quality of fit and the simplicity of the method proposed. These model would improve the accuracy of bioprocess scaling up.

An Experimental Kinetics Study of Isopropanol Pyrolysis and Oxidation behind Reflected Shock Waves

Isopropanol has potential as a future bio-derived fuel and is a promising substitute for ethanol in gasoline blends. Even so, little has been done in terms of high-temperature chemical kinetic speciation studies of this molecule. To this end, experiments were conducted in a shock tube using simultaneous CO and H2O laser absorption measurements. Water and CO formation during isopropanol pyrolysis was also examined at temperatures between 1127 and 2162 K at an average pressure of 1.42 atm. Species profiles were collected at temperatures between 1332 and 1728 K and at an average pressure of 1.26 atm for equivalence ratios of 0.5, 1.0, and 2.0 in highly diluted mixtures of 20% helium and 79.5% argon. Species profiles were also compared to four modern C3 alcohol mechanisms, including the impact of recent rate constant measurements. The Li et al. (2019) and Saggese et al. (2021) models both best predict CO and water production under pyrolysis conditions, while the AramcoMech 3.0 and Capriolo and Konnov models better predict the oxidation experimental profiles. Additionally, previous studies have collected ignition delay time (τign) data for isopropanol but are limited to low pressures in highly dilute mixtures. Therefore, real fuel–air experiments were conducted in a heated shock tube with isopropanol for stoichiometric and lean conditions at 10 and 25 atm between 942 and 1428 K. Comparisons to previous experimental results highlight the need for real fuel–air experiments and proper interpretation of shock-tube data. The AramcoMech 3.0 model over predicts τign values, while the Li et al. model severely under predicts τign. The models by Capriolo and Konnov and Saggese et al. show good agreement with experimental τign values. A sensitivity analysis using these two models highlights the underlying chemistry for isopropanol combustion at 25 atm. Additionally, modifying the Li et al. model with a recently measured reaction rate shows improvement in the model’s ability to predict CO and water profiles during dilute oxidation. Finally, a regression analysis was performed to quantify τign results from this study.

Photoinduced hole hopping through tryptophans in proteins

Hole hopping through tryptophan/tyrosine chains enables rapid unidirectional charge transport over long distances. We have elucidated structural and dynamical factors controlling hopping speed and efficiency in two modified azurin constructs that include a rhenium(I) sensitizer, Re(His)(CO)3(dmp)+, and one or two tryptophans (W1, W2). Experimental kinetics investigations showed that the two closely spaced (3 to 4 Å) intervening tryptophans dramatically accelerated long-range electron transfer (ET) from CuI to the photoexcited sensitizer. In our theoretical work, we found that time-dependent density-functional theory (TDDFT) quantum mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) trajectories of low-lying triplet excited states of ReI(His)(CO)3(dmp)+–W1(–W2) exhibited crossings between sensitizer-localized (*Re) and charge-separated [ReI(His)(CO)3(dmp•–)/(W1•+ or W2•+)] (CS1 or CS2) states. Our analysis revealed that the distances, angles, and mutual orientations of ET-active cofactors fluctuate in a relatively narrow range in which the cofactors are strongly coupled, enabling adiabatic ET. Water-dominated electrostatic field fluctuations bring *Re and CS1 states to a crossing where *Re(CO)3(dmp)+←W1 ET occurs, and CS1 becomes the lowest triplet state. ET is promoted by solvation dynamics around *Re(CO)3(dmp)+(W1); and CS1 is stabilized by Re(dmp•–)/W1•+ electron/hole interaction and enhanced W1•+ solvation. The second hop, W1•+←W2, is facilitated by water fluctuations near the W1/W2 unit, taking place when the electrostatic potential at W2 drops well below that at W1•+. Insufficient solvation and reorganization around W2 make W1•+←W2 ET endergonic, shifting the equilibrium toward W1•+ and decreasing the charge-separation yield. We suggest that multiscale TDDFT/MM/MD is a suitable technique to model the simultaneous evolution of photogenerated excited-state manifolds.

Kinetics and mechanism of oxidation of creatine by N-Bromosuccinimide in acidic aqueous medium

The kinetics and the mechanism of oxidation of creatine (AA) by N-Bromosuccinimide (NBS) in an acidic aqueous medium were examined under isolation conditions. Iodometric method was used to follow the unconsumed NBS at different time intervals. Mercuric(II) acetate was used as a scavenger to capture any Br- formed during the reaction and hence to avoid autocatalytic oxidation by bromine. Findings from stoichiometry measurements revealed that the reaction between AA and NBS was a 2:1 molar ratio. The kinetic study showed that the reaction was first order with respect to both AA and NBS. Increasing [H+] had a negative effect on the rate of reaction. The effect that varying the solvent composition has on the rate of reaction was investigated, and it was found that the reaction rate decreased as the dielectric constant of the solvent increased. The temperature dependence was determined under fixed experimental conditions, from which thermodynamic parameters were calculated. From the proposed mechanism, a rate law was established that was in strong agreement with experimental kinetics.

Bioconversion of Fish Discards through the Production of Lactic Acid Bacteria and Metabolites: Sustainable Application of Fish Peptones in Nutritive Fermentation Media

In the current work, we study the capacity of 30 peptones obtained by enzyme proteolysis of ten discarded fish species (hake, megrim, red scorpionfish, pouting, mackerel, gurnard, blue whiting, Atlantic horse mackerel, grenadier, and boarfish) to support the growth and metabolite production of four lactic acid bacteria (LAB) of probiotic and technological importance. Batch fermentations of Lactobacillus plantarum, L. brevis, L. casei, and Leuconostoc mesenteroides in most of the media formulated with fish peptones (87% of the cases) led to similar growths (quantified as dry-weight biomass and viable cells) and metabolites (mainly lactic acid) than in commercial control broth (MRS). Comparisons among cultures were performed by means of the parameters obtained from the mathematical fittings of experimental kinetics to the logistic equation. Modelling among experimental and predicted data from each bioproduction was generally accurate. A simple economic assessment demonstrated the profitability achieved when MRS is substituted by media formulated with fish discards: a 3–4-fold reduction of costs for LAB biomass, viable cells formation, and lactic and acetic acid production. Thus, these fish peptones are promising alternatives to the expensive commercial peptones as well as a possible solution to valorize discarded fish biomasses and by-products.

Metal Removal from Complex Copper Containing Effluents by Waste Biomass of Saccharomyces cerevisiae

Saccharomyces cerevisiae, waste biomass originated from beer fermentation industry, was used to remove metal ions from four copper-containing synthetic effluents: Cu-Fe, Cu-Fe-Ni, Cu-Fe-Zn, and Cu-Fe-Ni-Zn. The characterization of the biomass surface was investigated by Scanning Electron Microscopy and Fourier-transform Infrared Spectroscopy. The adsorption behavior of Saccharomyces cerevisiae for copper, iron, nickel and zinc ions in aqueous solution was studied as a function of pH, initial copper concentration, equilibrium time, and temperature. Langmiur, Freundlich, Temkin and Dubinin-Radushkevich equilibrium models have been assessed to describe the experimental sorption equilibrium profile, while pseudo-first order, pseudo-second order, Elovich and the intra-particle diffusion models were applied to describe experimental kinetics data. Maximum sorption capacities have been calculated by means of Langmuir equilibrium model and mean free sorption energies through the Dubinin-Radushkevich model. Thermodynamic analysis results showed that the adsorption of copper, iron and zinc was spontaneous and endothermic in nature, while of nickel exothermic. Saccharomyces cerevisiae can be successfully applied for complex wastewater treatment.

CO2 Conversion to Methanol over Novel Carbon Nanofiber-Based Cu/ZrO2 Catalysts—A Kinetics Study

Ongoing industrialization has deteriorated the global environment. Global warming is a human-induced issue affecting the environment. The alarming increase in CO2 emissions is among the major contributors to global warming. The conversion of CO2 to methanol is an economically viable and environmentally friendly solution to mitigate its concentration. Here, hydrogenation of CO2 was studied over carbon nanofiber-based Cu/ZrO2 catalysts. Kinetics investigations were carried out for the reaction. Overall, kinetics data indicated that CO2 conversion follows a pseudo-first-order reaction. The kinetics studies were further modeled by using an artificial neural network, which supported the experimental kinetics study.