Ateyya A. Aboul-Enein

Para-Xylene Maximization. Part VIII: Promotion of H-ZSM-5 Zeolite by Pt and HF Doping for Use as Catalysts in Toluene Alkylation with Methanol

Toluene was alkylated with methanol in a flow type reactor at temperatures between 300 and 500℃ using H-ZSM-5 zeolite, 0.2%Pt/H-ZSM-5 and hydrofluorinated 0.2%Pt/H-ZSM-5 with HF concentrations of 1.0%, 2.0%, 3.0%, or 4.0%. Pt primarily enhances toluene conversion, total xylenes production, and p-xylene relative to its thermodynamic equilibrium. As the concentration of HF increases from 1.0% to 3.0%, the catalyst activity increases because of the increase in the number of acid sites and their strength. Additionally, the surface area and Pt dispersion also increases. An advantage of increased HF doping is that the formation of voluminous trimethylbenzene (TMB) byproducts is inhibited. However, at a HF concentration of 4.0%, Al and Si are partially leached and then deposited mostly in the wider catalytic pores. This was determined by evaluating the pore volume distribution and we determined that reactivity inhibition was obviously present and was due to diffusion restriction.

Catalytic Decomposition of Natural Gas to CO/CO2-Free Hydrogen Production and Carbon Nanomaterials Using MgO-Supported Monometallic Iron Family Catalysts

Monometallic Fe, Co, and Ni/MgO catalysts with 50 wt.% metal loadings were prepared and examined for natural gas decomposition to nanocarbonaceous materials, particularly multiwalled carbon nanotubes (MWCNTs) and co-valuable hydrogen. The catalytic testing was carried out in a fixed-bed horizontal reactor at 700°C under atmospheric pressure. The fresh and/or used catalysts were characterized using XRD, TPR, HRTEM, SEM, TG/DTA, Raman spectroscopy, and BET surface measurements. The resulting data showed that the 50%Co/MgO catalyst displayed higher catalytic decomposition activity of natural gas to COx-free hydrogen production (∼88%), higher yield of MWCNTs, and excellent stability up to 10 h time-on-stream. On the other hand, the Ni-containing catalyst showed lower catalytic activity toward hydrogen and CNTs production, principally due to the formation of rock-salt MgxNi(1-x)O solid solution as observed from XRD and TPR data. Accordingly, the concentration of Ni particles required for natural gas feed was extremely low. The d orbital of Ni was presumed to be occupied during the formation of the solid solution, which inhibits the solublization or adsorption of hydrocarbons on Ni particles. The MWCNTs obtained over Ni-based catalyst had narrow and homogeneous diameters (∼11–13 nm). However, the Fe/MgO catalyst exhibited intermediate activity between those of Ni and Co˭MgO catalysts toward hydrogen production (∼44%). This catalyst produced mixtures of carbon nanofibers and nanotubes.

Effect of structural promoters on the catalytic performance of cobalt-based catalysts during natural gas decomposition to hydrogen and carbon nanotubes

ABSTRACT Catalytic thermal decomposition of natural gas to CO/CO2-free hydrogen production was studied over cobalt catalysts supported on Al2O3, MgO, and SiO2. The physico-chemical properties of the fresh catalysts were investigated by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and surface area. In addition, the morphological structure of as-deposited carbon over the spent catalysts was characterized by transmission electron microscope (TEM), Raman spectroscopy, thermogravimetric analysis, and XRD. The obtained results proved that the catalytic activity and longevity of the cobalt-based catalysts strongly depended on the nature of the applied support. Among the catalysts tested, the Co/Al2O3 catalyst exhibited the highest activity and stability due to the higher dispersion and stabilization of cobalt particles because of formation of CoAl2O3 spinel phase. The lower activity of Co/SiO2 catalyst is mainly attributed to the aggregation of cobalt metal particles because of weak metal–support interaction. It was observed that both type and morphological structure of deposited carbon were strictly depended on the nature of the support. TEM images revealed that multi-walled carbon nanotubes were produced over Al2O3- and MgO-supported catalysts, whereas both carbon nanofibers and amorphous carbon were formed over the Co/SiO2 catalyst.

Simple method for synthesis of carbon nanotubes over Ni-Mo/Al2O3 catalyst via pyrolysis of polyethylene waste using a two-stage process

ABSTRACT Synthesis of valuable multi-walled carbon nanotubes (MWCNTs) by thermal pyrolysis of low-density polyethylene (LDPE) waste was investigated via a two-stage process. The first stage was the thermal pyrolysis of LDPE to gaseous hydrocarbons, and the second stage was the catalytic decomposition of the pyrolysis gases over Ni-Mo/Al2O3 catalysts. Two catalysts with the compositions of 5.2%Ni-10.96%Mo/Al2O3 and 10%Ni-9.5%Mo/Al2O3 were tested for carbon nanotubes (CNTs) formation. The catalyst containing 10%Ni showed better activity in terms of CNTs production. Accordingly, the impact of either pyrolysis or decomposition temperatures was investigated using the 10%Ni-9.5%Mo/Al2O3 catalyst. TEM, XRD, Raman spectroscopy, TGA, TPR, and BET analysis tools were used to characterize the fresh catalysts as well as the obtained carbon nanomaterials. TEM images proved that MWCNTs with various morphological structures were obtained at all pyrolysis and decomposition temperatures. Moreover, cup-stacked carbon nanotubes (CS-CNTs) were observed at the decomposition temperature of 600°C. MWCNTs with the best quality were produced at decomposition temperature of 750°C. The optimum pyrolysis and decomposition temperatures in terms of CNTs production were at 700 and 650°C, respectively.

Influence of Mo or Cu doping in Fe/MgO catalyst for synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of methane

ABSTRACT A series of mono-, bi- or tri-metallic Fe–Mo-Cu/MgO catalysts with the same metal loading of 6 wt% were prepared by impregnation method and used as catalysts for synthesis single-walled carbon nanotubes (SWCNTs) via methane decomposition. XRD, H2-TPR, and nitrogen physisorption techniques were used to characterize the freshly calcined catalysts, while HRTEM, Raman spectroscopy and TGA were employed to investigate the morphology and microstructure of the SWCNTs product. The obtained results indicated that the introduction of Mo or Cu in the Fe/MgO catalyst enhanced the catalytic growth activity. TEM images showed that both bundles and isolated SWCNTs were obtained over Mo containing catalysts, whereas only SWCNTs bundles were grown over the Fe-Cu/MgO catalyst. The obtained SWCNTs having a diameter of around 0.9–2.4 nm. Raman analysis illustrated that all promoted catalysts produced high quality of SWCNTs compared to the unpromoted Fe/MgO catalyst.

Direct Conversion of Natural Gas to Petrochemicals Using Monofunctional Mo/SiO2 and H-ZSM-5 Zeolite Catalysts and Bifunctional Mo/H-ZSM-5 Zeolite Catalyst

Abstract The components of the standard catalyst globally used for natural gas direct conversion (6% Mo/H-ZSM-5) have been separately prepared and examined to represent: (a) monofunctional metallic component (6% Mo/SiO2) and (b) acidic component (H-ZSM-5 zeolite) to numerically investigate the extent of activity of each catalytic component in comparison to the activity of the standard catalyst in a fixed-bed flow-type reactor. The temperature and gas hourly space velocity are 700°C and 1500 mLg−1 h −1, respectively, which are very close to those used in the industrial gas conversion reactions. Time on stream up to 240 min was examined. The gaseous products were ethylene, propylene, and hydrogen, whereas the liquid products were benzene, toluene, and naphthalene. Carbon was also produced as deposited particles on the catalyst.

Correlation Between Periodicity and Catalytic Growth Activity of Bimetallic Co-group VI/MgO Catalysts for Production of Carbon Nanotubes by Acetylene Using Chemical Vapor Deposition

This work aims to discover a relationship between the periodicity and catalytic growth activity of carbon nanotubes by acetylene chemical vapor deposition. Hence, the effect of addition of group VI metals (25% of Cr, Mo, or W) of the periodic table to 25 wt% Co supported on MgO has been investigated. The fresh catalysts and carbon nanomaterials were characterized by XRD, TPR, TEM, Raman spectroscopy, BET surface measurements, and TG analysis. The results revealed that the addition of group VI metals induces a strong interaction with the structural MgO crystals associated with an enhancement in surface properties. XRD data shows that the appearance of group VI metal oxides in the diffraction patterns primarily dependent on the corresponding atomic weights. TGA data shows that the Co–W/MgO catalyst exhibited higher carbon nanotubes (CNTs) yield compared to the Co–Cr or Co–Mo containing catalysts. The yield of CNTs increases gradually with increasing the atomic weight of group VI metals (W > Mo > Cr). This finding can be attributed to the higher surface coverage of Co-W/MgO and consequently the larger amount of metal sites which are responsible for the higher yield of MWCNTs compared to the other bimetallic catalysts. The higher metallic surface permits decomposing a larger amount of C2H2 molecules more efficiently. XRD, TEM, and Raman spectroscopic data revealed that highly graphitized MWCNTs were produced over all catalysts under study.

Reactions of Cyclohexane on Platinum, Palladium, or Iridium-loaded H-ZSM-5 Zeolite Hydrohalogenated Catalysts

Abstract The catalytic hydroconversion of cyclohexane using catalysts containing H-ZSM-5 zeolite loaded with 0.35 wt% platinum, palladium, or iridium was studied in a pulse-type microreactor/GC system at atmospheric pressure. These catalysts were also either doped with 3.0% of HCl or HF. The activities of these catalysts and the distribution of the products formed were found to depend on the dispersion of the metallic component as well as on the acidity, acid sites number, and strength in the catalysts. TPD of ammonia and hydrogen chemisorption were applied to evaluate acid site strength distribution and metals dispersion, respectively, in the catalysts. In case of the Pt- and Pd-containing catalysts, hydrochlorination enhanced the isomerization and dehydrogenation activities and selectivities of cyclohexane, but decreased its hydrocracking activity. However, catalyst hydrofluorination resulted in the reverse effects. Nevertheless, for the Ir-loaded catalyst, both hydrohalogenation treatments decreased the isomerization and dehydrogenation of cyclohexane. The Ir/H-ZSM-5 catalyst exhibited higher hydrogenolysis activities than did those acquired by the Pt- and Pd-containing catalysts.

ZrxMg1-xO supported cobalt catalysts for methane decomposition into COx-free hydrogen and carbon nanotubes

ABSTRACT Zirconia-magnesia supported cobalt catalysts with various Zr/Mg atomic ratios were prepared and evaluated for non-oxidative catalytic decomposition of methane to produce COx-free hydrogen and carbon nanotube. The catalytic performance of the catalysts was performed in a continuous fixed bed flow reactor at 700°C under atmospheric pressure. The fresh and spent catalysts were characterized by XRD, TPR, BET, TEM, and Raman spectroscopy. The results showed that the change in Zr/Mg ratio of the mixed oxide support has a significant effect on the catalytic performance of the active Co metal. The catalyst 30%Co/Zr0.8Mg0.2 showed the highest activity and stability within the used series of catalysts with hydrogen yield reached up to 79%. Both Co/Mg1.0 and Co/Zr1.0 showed poor stability due to strong Co-Mg interaction and aggregation of Co species on Zr support, respectively. All catalysts produced mainly MWCNTs with different diameters depending on the Zr/Mg ratio. The outer diameter increased with increasing Zr content in the catalyst due to the enlargement of the particle size of cobalt as a result of aggregation.