Hydrogenation of pyrolysis gasoline by novel Ni-doped MOF derived catalysts from ZIF-8 and ZIF-67.

Pyrolysis gasoline is the valuable byproduct of the thermal breakdown of heavier oil fractions in an olefin unit with high aromatic content. To separate such aromatic components, firstly, this product should be hydrogenated. In this contribution, new nanostructure catalysts derived from the zeolitic metal-organic framework, namely ZIF-8 and ZIF-67, were used to investigate their hydrogenation capability. Owing to its great hydrogenation capability of Nickle, the structures of the ZIF-8 and ZIF-67 were improved by Nickle through in situ synthesis. Moreover, to enhance the pore size of catalysts and their electronic properties, the synthesized catalysts were pyrolyzed under nitrogen media at 450 °C, and five catalysts, namely Co/NC, ZnCo/NC, ZnNi/NC, CoNi/NC, and ZnCoNi/NC were created. Results indicated that the CoNi/NC showed a superior hydrogenation performance (69.5% conversion of total olefins) to others. In addition, the synthesized catalysts without the carbonization process had no conversion in the hydrogenation process because there is no active site in these structures. The current synthesized catalysts can compete with the costly Pt or Pd-based hydrogenation catalysts due to their high surface area and great electronic properties.

On the evaluation of hydrogen evolution reaction performance of metal-nitrogen-doped carbon electrocatalysts using machine learning technique.

Single-atom catalysts (SACs) introduce as a promising category of electrocatalysts, especially in the water-splitting process. Recent studies have exhibited that nitrogen-doped carbon-based SACs can act as a great HER electrocatalyst. In this regard, Adaptive Neuro-Fuzzy Inference optimized by Gray Wolf Optimization (GWO) method was used to predict hydrogen adsorption energy (ΔG) obtained from density functional theory (DFT) for single transition-metal atoms including Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, and Au embedded in N-doped carbon of different sizes. Various descriptors such as the covalent radius, Zunger radius of the atomic d-orbital, the formation energy of the single-atom site, ionization energy, electronegativity, the d-band center from - 6 to 6 eV, number of valence electrons, Bader charge, number of occupied d states from 0 to - 2 eV, and number of unoccupied d states from 0 to 2 eV were chosen as input parameters based on sensitivity analysis. The R-squared and MSE of the developed model were 0.967 and 0.029, respectively, confirming its great accuracy in determining hydrogen adsorption energy of metal/NC electrocatalysts.

Bandgaps of noble and transition metal/ZIF-8 electro/catalysts: a computational study.

Zeolitic imidazolate frameworks (ZIFs) are designed with metals as center atoms, connected by imidazole-like linkers. The created structures have been employed considerably in the field of advanced energy materials, including catalysis/electrocatalysis and energy storage and harvesting applications. In the present study, the bandgaps of pristine and doped ZIF-8 (using noble and transition metal dopants such as Pd, Pt, Ni, Mn, Co, Cu, Fe, and Ti) are determined. This can result in a promising approach to enhance the corresponding electronic properties while applying noble metal-free dopants. To determine the bandgap values, a quantum mechanical modeling based on density functional theory (DFT) was applied. Then, due to the time-consuming and complicated nature of this approach, the obtained results from the DFT study were then employed to develop the support vector machine (SVM) model to estimate the bandgap of the resulting nanostructure. The outcomes of the proposed model showed its high accuracy, with R 2 of 0.98 and root mean squared error (RMSE) of 0.04. The developed model could have great value in designing various ZIF-8-based nanostructures, particularly when applied in electro/catalytic reactions, e.g., electrocatalytic hydrogen evolution reaction or catalytic hydrogenation reaction, through a simple approach.

Modeling of microalgal shear-induced flocculation and sedimentation using a coupled CFD-population balance approach.

In this study, shear-induced flocculation modeling of Chlorella sp. microalgae was conducted by combination of population balance modeling and CFD. The inhomogeneous Multiple Size Group (MUSIG) and the Euler-Euler two fluid models were coupled via Ansys-CFX-15 software package to achieve both fluid and particle dynamics during the flocculation. For the first time, a detailed model was proposed to calculate the collision frequency and breakage rate during the microalgae flocculation by means of the response surface methodology as a tool for optimization. The particle size distribution resulted from the model was in good agreement with that of the jar test experiment. Furthermore, the subsequent sedimentation step was also examined by removing the shear rate in both simulations and experiments. Consequently, variation in the shear rate and its effects on the flocculation behavior, sedimentation rate and recovery efficiency were evaluated. Results indicate that flocculation of Chlorella sp. microalgae under shear rates of 37, 182, and 387 s-1 is a promising method of pre-concentration which guarantees the cost efficiency of the subsequent harvesting process by recovering more than 90% of the biomass. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 34:160-174, 2018.

Synechococcus sp. (PTCC 6021) cultivation under different light irradiances-Modeling of growth rate-light response.

Synechococcus sp. (PTCC 6021), a cyanobacterium species, was cultivated in an internally illuminated photobioreactor. The reactor was designed to achieve a monoseptic cultivation of the species. The goal was to study the growth-irradiance behavior of Synechococcus sp. (PTCC 6021). To accomplish this, different initial light irradiances were implemented inside the photobioreactor and the growth of the cells was monitored. It was observed that cell growth increased with higher light intensity until the photoinhibition occurrence at light irradiance higher than 250 µE m(-2) s(-1). The maximum OD600, maximum growth rate, and biomass productivity increased, and hence the extinction coefficient decreased, with the increase in light irradiance before photoinhibition. The maximum optical density (OD600) of 5.91 was obtained with irradiance below 250 µE m(-2) s(-1) during a growth period of 80 days. The modified Monod function could model the growth-irradiance of cells with satisfactory agreement with the experimental data. The comparison of growth-irradiance of the studied species with other photosynthetic organisms showed the same trend as for cyanobacteria with photoinhibition.

Response surface methodology for the modeling and optimization of oil-in-water emulsion separation using gas sparging assisted microfiltration.

Response surface methodology (RSM) and central composite design (CCD) were used to develop models for optimization and modeling of a gas sparging assisted microfiltration of oil-in-water (o/w) emulsion. The effect of gas flow rate (Q G ), oil concentration (C oil ), transmembrane pressure (TMP), and liquid flow rate (Q L ) on the permeate flux and oil rejection were studied by RSM. Two sets of experiments were designed to investigate the effects of different gas-liquid two-phase flow regimes; low and high gas flow rates. Two separate RSM models were developed for each experimental set. The oil concentration and TMP were found to be the most significant factors influencing both permeate flux and rejection. Also, the interaction between these parameters was the most significant one. At low Q G , the more the gas flow rate, the higher the permeate flux; however, in the high gas flow rate region, higher Q G did not necessarily improve the permeate flux. In the case of rejection, gas and liquid flow rates were found to be insignificant. The optimum process conditions were found to be the following: Q G = 1.0 (L/min), C oil = 1,290 (mg/L), TMP = 1.58 (bar), and Q L = 3.0 (L/min). Under these optimal conditions, maximum permeate flux and rejection (%) were 115.9 (L/m(2)h) and 81.1 %, respectively.