Synthesis and Characterization of NiMo Catalysts Supported on Fine Carbon Particles for Hydrotreating: Effects of Metal Loadings in Catalyst Formulation

The by-products collected during the synthesis of carbon nanohorns via the arc discharge synthesis method is comprised of other carbon particles (OCP). At a hydrotreating operating temperature of 370°C, preliminary investigations using a bimetallic catalyst with support originating from the fine fractions of other carbon particles (OCPf) and containing 13 wt% Mo and 2.5 wt% Ni resulted in an HDS and HDN conversion of 78 and 25%, respectively. Variation of metal compositions in catalyst formulation and its impact on hydrotreating activity was therefore considered in this study to enhance the hydrotreating activity of OCPf–supported catalyst, and to determine if the best NiMo/OCPf catalyst achieved from this study could be a viable catalyst for hydrotreating applications. The co-incipient wetness impregnation was used in preparing series of hydrotreating catalysts with Ni and Mo loadings within the range of (2.5–5.0 wt%) and (13–26 wt%) respectively. Overall, the catalyst samples with maximum Ni loading of 5.0 wt% and Mo loadings of either 13 or 19 wt% showed higher dispersion and the ability to form a Type II Ni-Mo-S phase with enhanced activity. The effects of metal compositions on both HDS and HDN activities were correlated with their physicochemical properties.

Biofuel from hydrocracking of Cerbera manghas oil over Ni-Zn/HZSM-5 catalyst

The effects of reaction temperature on the hydrocarbon composition of biofuel produced in hydrocracking of Cerbera manghas oil with Ni-Zn/HZSM-5 catalyst were investigated. The incipient wetness impregnation method was applied to prepare the Ni-Zn/HZSM-5 catalysts. Furthermore, the properties of catalysts were measured by X-ray diffraction, atomic absorption spectrometry, and nitrogen physisorption. Hydrocracking process was carried out in Parr USA pressure batch reactor at pressure of 20 � 5 bar after flowing H2 for 1 h. The reaction with a catalyst/oil ratio of 1 g/150 mL proceeded at various temperatures of 350, 375 and 400 �C for 2 h. Gas chromatography-mass spectrometry was�used to analyze biofuel. The most abundant hydrocarbon compounds in biofuel were identified as pentadecane and heptadecane (a major diesel fuel compound) with a different amount at different reaction temperatures. It can be said that the hydrodecarboxylation/decarbonylation routes were the predominant reaction pathways and oxygen removal occurred during hydrocracking. The Cerbera manghas oil can be recommended as a promising biofeed to produce the gasoil as an alternative transportation fuel.

Cobalt oxide enhanced lanthanum strontium cobalt ferrite electrode for solid oxide fuel cells

A Co3O4 enhanced La0.8Sr0.2Co0.5Fe0.5O3 - δ (LSCF) electrode is developed for use in air electrodes with proton conducting solid oxide fuel cell (SOFC). The incipient wetness impregnation method enables Co3O4 nanoparticles on the LSCF surface without altering the bulk porosity of the LSCF electrode. The polarization resistance of LSCF electrodes is significantly reduced by Co3O4 doping, and both charge transfer and diffusion/conversion resistances were positively affected. The highest reduction in charge transfer resistance is obtained at 700 °C, which is increased from 21%to 32%through reduction of po 2. Conversely, the highest reduction in diffusion/conversion resistance is achieved at 550 °C. By increasing po 2, the reduction is increased from 57%to 66%and its activation energy is reduced up to 33 %compared to pure LSCF. The lowest total area specific resistances obtained under air are 1.45 Ω·cm2, 2.95 Ω·cm2, 6.75 Ω·cm2 and 16.45 Ω·cm2 at 700 °C, 650 °C, 600 °C and 550 °C, respectively.

Biofuel production over Fischer-Tropsch synthesis: effect of Fe-Co/meso-HZSM-5 catalyst weight on product composition and process conversion

Fischer-Tropsch Synthesis (FTS) using Fe-Co/meso-HZSM-5 catalyst has been investigated. The impregnated iron and cobalt on HZSM-5 could be used as bifunction catalyst which combined polimerizing synthesis gas and long hydrocarbon cracking for making biofuel (saturated C5–C25 hydrocarbons as gasoline, kerosene and diesel oil). The study emphasized the effect of catalyst weight on product composition and process conversion. The HZSM-5, had been converted from ammonium ZSM-5 through calcination, and then desilicated with NaOH solution. The Co(NO3)2.6H2O and Fe(NO3)3.9H2O were used as precursor for incipient wetness impregnation (IWI) on amorphous meso-HZSM-5. The catalyst consisted of 10 % Fe and 90 % Co by weight, called 10Fe-90Co/meso-HZSM-5. All catalysts were reduced in situ in the continuous reactor with flowing hydrogen at 25 mL/min, 1 bar, 400 °C for 10 hours. The catalyst performance was observed in the same continuous fixed bed reactor at 25 mL/min synthesis gas (30 % CO, 60 % H2, 10 % N2), 250 °C, 20 bar for 96 hours. Various catalyst weight (1, 1.2, 1.4, 1.6 gram) were applied in FTS. The desilicated HZSM-5 properties (BET analysis) were 6.1–29.9 nm mesoporous diameter, 0.3496 cc/g average mesoporous volume, 526.035 cc/g pore surface area, and the EDX analysis gave 22.1059 Si/Al ratio and 16.11 % loading (by weight) on meso-HZSM-5. The reduced catalyst showed the XRD spectra of Fe (66°), Fe-Co alloy (44.50°) and Co3O4 (36.80°). The reaction using 1 gram of 10Fe-90Co/meso-HZSM-5 catalyst produced the largest composition and conversion. The 1 gram catalyst gave the largest normal selectivity of gasoline (19.15 %) and kerosene (55.18 %). While the largest normal diesel oil selectivity (24.17 %) was obtained from 1.4 gram of catalyst. The CO conversion per gram of catalyst showed similar value (CO conversion of 26–28 %) for all catalyst weight

Polyelectrolyte-Coated Mesoporous Bioactive Glasses via Layer-by-Layer Deposition for Sustained Co-Delivery of Therapeutic Ions and Drugs

In the field of bone regeneration, considerable attention has been addressed towards the use of mesoporous bioactive glasses (MBGs), as multifunctional therapeutic platforms for advanced medical devices. In fact, their extremely high exposed surface area and pore volume allow to load and the release of several drugs, while their framework can be enriched with specific therapeutic ions allowing to boost the tissue regeneration. However, due to the open and easily accessible mesopore structure of MBG, the release of the incorporated therapeutic molecules shows an initial burst effect leading to unsuitable release kinetics. Hence, a still open challenge in the design of drug delivery systems based on MBGs is the control of their release behavior. In this work, Layer-by-layer (LbL) deposition of polyelectrolyte multi-layers was exploited as a powerful and versatile technique for coating the surface of Cu-substituted MBG nanoparticles with innovative multifunctional drug delivery systems for co-releasing of therapeutic copper ions (exerting pro-angiogenic and anti-bacterial effects) and an anti-inflammatory drug (ibuprofen). Two different routes were investigated: in the first strategy, chitosan and alginate were assembled by forming the multi-layered surface, and, successively, ibuprofen was loaded by incipient wetness impregnation, while in the second approach, alginate was replaced by ibuprofen, introduced as polyelectrolyte layer. Zeta-potential, TGA and FT-IR spectroscopy were measured after the addition of each polyelectrolyte layer, confirming the occurrence of the stepwise deposition. In addition, the in vitro bioactivity and the ability to modulate the release of the cargo were evaluated. The polyelectrolyte coated-MBGs were proved to retain the peculiar ability to induce hydroxyapatite formation after 7 days of soaking in Simulated Body Fluid. Both copper ions and ibuprofen were co-released over time, showing a sustained release profile up to 14 days and 24 h, respectively, with a significantly lower burst release compared to the bare MBG particles.

Bimetallic Cu/Fe Catalysts for Ibuprofen Mineralization

At present, the use of conventional wastewater processes is becoming increasingly challenging, mainly due to the presence of biorecalcitrant organic matter. Advanced oxidation processes such as Fenton, Fenton-like and hybrid processes have been successfully employed for the treatment of highly concentrated and toxic non-biodegradable pollutants. Here, a series of bimetallic catalysts, based on Cu/Fe supported over ZrO2, were investigated for the mineralization of ibuprofen with a heterogeneous Fenton-like reaction. The materials were prepared by incipient wetness impregnation and characterized by standard techniques. Temperature-programmed experiments highlighted the promotion of the reduction in CuO due to the synergistic effects of the coupled redox cycles of copper (Cu2+/Cu+) and iron (Fe+3/Fe+2). 5%Cu-5%Fe/ZrO2 not only displays the highest ibuprofen mineralization (83%) under optimum conditions but also exploits its activity in a wider range of pH (3–5) with extremely low metal leaching. The recycling of bimetallic catalysts reveals that only the 5%Cu-5%Fe/ZrO2 system is able to provide sustainable activity in heterogeneous Fenton process.

Low-Temperature Selective Catalytic Reduction DeNOX and Regeneration of Mn–Cu Catalyst Supported by Activated Coke

The activated coke is a promising support for catalysts, and it is important to study the performance of the activated coke catalyst on the removal of NOx. In the current research, a series of the activated coke-supported Mn–Cu catalysts are prepared by the incipient wetness impregnation method. The effects of the molar ration of Mn/Cu, the content of Mn–Cu, the calcination temperature, and reaction space velocity on NO conversion are investigated, and it was found that the 8 wt.% Mn0.7Cu0.3/AC had the best catalytic activity when the calcination temperature was 200 °C. The existence of SO2 caused the catalyst to deactivate, but the activity of the poisoning catalyst could be recovered by different regeneration methods. To uncover the underlying mechanism, BET, XPS, XRD, SEM and FTIR characterizations were performed. These results suggested that the specific surface area and total pore volume of the poisoning catalyst are recovered and the sulfite and sulfate on the surface of the poisoning catalysts are removed after water washing regeneration. More importantly, the water washing regeneration returns the value of Mn3+/Mn4+, Cu2+/Cu+, and Oα/Oβ, related to the activity, basically back to the level of the fresh catalyst. Thus, the effect of water washing regeneration is better than thermal regeneration. These results could provide some helpful information for the design and development of the SCR catalysts.

Synthesis of Nickel-loaded Sulfated Zirconia Catalyst and Its Application for Converting Used Palm Cooking Oil to Gasoline via Hydrocracking Process

The synthesis of the nickel-loaded sulfated zirconia catalyst (Ni-SZ) and its application for the hydrocracking process have been carried out. This work has been conducted to determine the activity and selectivity from various Ni concentrations loaded on sulfated zirconia (SZ) in the hydrocracking of used palm cooking oil. The synthesis technique was preceded by sulfation of ZrO2 through incipient wetness impregnation method using H2SO4 solution and then continued with the impregnation of Ni via hydrothermal method employing NiSO4 · 6H2O precursor salt. The hydrocracking process was performed in a fix-bed microreactor at the optimum temperature (350 °C). The SZ loaded with 3 wt% of Ni (Ni-SZ 3) successfully produced the highest liquid product (44.25 wt%) and selectivity on gasoline (100 %). Besides, the gasoline fraction in the liquid product was dominated by unwanted aromatics compounds. The excellent performance of Ni-SZ 3 due to it has high acidity value, specific surface area, and Ni content.

Mutual inhibition effect of sulfur compounds in the hydrodesulfurization of thiophene, 2-ethylthiophene and benzothiophene ternary mixture

The hydrodesulphurization of a model component and equimolar ternary mixture of thiophene, 2-ethylthiophene and benzothiophene over sulphided CoMo/γ-Al2O3 and CoMo/γ-Al2O3-Nb2O5 catalysts were investigated in a fixed bed flow reactor. The catalysts were prepared by incipient wetness impregnation method and characterized by textural characteristics, total acidity and chemical species present on the catalysts surface. The characterization results showed that both CoMo/γ-Al2O3-Nb2O5 and sulphided CoMo/γ-Al2O3 catalysts exhibit a mesoporous structure with cylindrical pores open at both ends, evidenced by the IV type adsorption–desorption isotherm with a H1 hysteresis loop and have an average pore diameter between 3 and 4 nm. The chemical species present on the catalysts surface evaluated by XPS indicated that Co2+ and Mo4+ species are present in the sulfide form on both catalysts surfaces. In addition, there are also found oxidic species arising from incomplete reduction and sulphidation. The presence of niobium oxide in the catalytic support had a positive effect in leading to higher specific surface area (170 m2/g) and total acidity (0.421 meq/g) compared with CoMo/γ-Al2O3 catalyst (140 m2/g and 0.283 meq/g) respectively. The evaluation results from the hydrodesulfurization showed that CoMo/γ-Al2O3-Nb2O5 catalyst had a higher activity in hydrodesulphurization process of thiophene, 2-ethylthiophene and benzothiophene. The CoMo/γ-Al2O3-Nb2O5 catalyst eliminated sulfur from the single component feed (corresponding to 2380 ppm S) and reduced below 10 ppm, for the feed consisting in the equimolar ternary mixture of thiophene, 2-ethylthiophene and benzothiophene (2380 ppm S). The reactivity of thiophen compounds was reduced due to competitive adsorption. It was observed that benzothiophene inhibits the transformation of thiophene and 2-ethylthiophene. A mutual inhibition effect between sulfur compounds was also observed when thiophene, 2-ethylthiophene and benzothiophene were combined and tested over the CoMo/γ-Al2O3 catalyst. The inhibition effect had a lower intensity by introducing Nb2O5 in the catalyst support.

Well-Dispersed MgAl2O4 Supported Ni Catalyst with Enhanced Catalytic Performance and the Reason of Its Deactivation for Long-Term Dry Methanation Reaction

Dry methanation of syngas is a promising route for synthetic natural gas production because of its water and cost saving characteristics, as we reported previously. Here, we report a simple soaking process for the preparation of well-dispersed Ni/MgAl2O4-E catalyst with an average Ni size of 6.4 nm. The catalytic test results showed that the Ni/MgAl2O4-E catalyst exhibited considerably higher activity and better stability than Ni/MgAl2O4-W catalyst prepared by conventional incipient wetness impregnation method in dry methanation reaction. The long-term stability test result of 335 h has demonstrated that the deactivation of the Ni/MgAl2O4-E catalyst is inevitable. With multiple characterization techniques including ICP, EDS, XRD, STEM, TEM, SEM and TG, we reveal that the graphitic carbon encapsulating Ni nanoparticles are the major reasons responsible for catalyst deactivation, and the rate of carbon deposition decreases with reaction time.