The application of calcined natural dolomitic rock as a solid base catalyst in triglyceride transesterification for biodiesel synthesis

Natural dolomitic rock has been investigated in the transesterification of C-4 and C-8 triglycerides and olive oil with a view to determining its viability as a solid base catalyst for use in biodiesel synthesis. XRD reveals that the dolomitic rock comprised 77% dolomite and 23% magnesian calcite. The generation of basic sites requires calcination at 900 degrees C, which increases the surface area and transforms the mineral into MgO nanocrystallites dispersed over CaO particles. Calcined dolomitic rock exhibits high activity towards the liquid phase transesterification of glyceryl tributyrate and trioctanoate, and even olive oil, with methanol for biodiesel production.

Unraveling the synergy between gold nanoparticles and chromium- hydrotalcites in aerobic oxidation of alcohols

The combination of gold nanoparticles (AuNPs) with chromium-substituted hydrotalcite (Cr-HT) supports makes very efficient heterogeneous catalysts (Au/Cr-HT) for aerobic alcohol oxidation under soluble-base-free conditions. The Au-support synergy increases with increasing Cr content of the support and decreasing AuNP size. In situ UV-Raman, X-ray absorption and photoelectron spectroscopic studies firmly establish that the strong Au-Cr synergy is related to a Cr ↔ Cr redox cycle at the Au/Cr-HT interface, where O activation takes place accompanied by electron transfer from Cr-HT to Au. The interfacial Cr species can be reduced by surface Au-H hydride and negative-charged Au species to close the catalytic cycle. A study of kinetic isotope effect indicates that alcohol O-H cleavage is facilitated by the presence of Cr, making a-C-H bond cleavage step more rate-controlling. Accordingly, a dual synergistic effect of Au/Cr-HT catalysts on the activation of O2 and alcohol reactants is proposed.

Ionic liquids as solvent and solvent additives for the synthesis of sol-gel materials

The ionic liquid (IL) 1-butyl-3-methylimidazolium chloride was used as a drying control chemical additive in the synthesis of silica sol-gel materials with and without methanol as a co-solvent. The resulting gels were characterized by using thermogravimetric analysis, differential scanning calorimetry, infrared spectroscopy and water sorption kinetics. Calcined gels were analyzed using scanning electron microscopy and nitrogen adsorption isotherms for surface area and pore volume determination. Non-calcined gels were monolithic and showed general cloudiness with lesser degrees observed at higher IL volumes. Calcinations resulted in the formation of powders with increased available surface area as the amount of IL volume was increased. This is consistent with an increase in respective pore volume but a general decrease in average pore size. The resulting materials exhibited conventional structural microdomains, in contrast to periodicity reported when other ionic liquids were used as templates.

Structural and magnetic properties of sol-gel Co2xNi0.5-xZn0.5-xFe2O4 thin films

Nanocrystalline Co2xNi0.5-xZn0.5-xFe2O4 (x = 0-0.5) thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology as well as magnetic and microwave absorption properties of the films calcined at 1073 K were studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. All films were uniform with out microcracks . The Co content in the Co-Ni-Zn films resulted in a grain size ranging from 15 to 32 nm while it ranged from 33 to 49 nm in the corresponding powders. Saturation and remnant magnetization increased with increase in grain size, while coercivity demonstrated a drop due to multidomain behavior of crystallites for a given value of x. Saturation magnetization increased and remnant magnetization had a maximum as a function of grain size in dependent of x. In turn, coercivity increased with x independent of grain size. Complex permittivity of the Co-Ni-Zn ferrite films was measured in the frequency range 2-15 GHz. The highest hysteretic heating rate in the temperature range 315-355 K was observed in CoFe2O4. The maximum absorption band shifted from 13 to 11GHz as cobalt content increased from x = 0.1 to 0.2.

Structural investigations and magnetic properties of sol-gel Ni0.5Zn0.5Fe2O4 thin films for microwave heating

Nanocrystalline Ni0.5Zn0.5Fe2O4 thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology, magnetic, and microwave absorption properties of the films calcined in the 673-1073 K range were studied with x-ray diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, vibrating sample magnetometry, and evanescent microwave microscopy. All films were uniform without microcracks. Increasing the calcination temperature from 873 to 1073 K and time from 1 to 3 h resulted in an increase of the grain size from 12 to 27 nm. The saturation and remnant magnetization increased with increasing the grain size, while the coercivity demonstrated a maximum near a critical grain size of 21 nm due to the transition from monodomain to multidomain behavior. The complex permittivity of the Ni-Zn ferrite films was measured in the frequency range of 2-15 GHz. The heating behavior was studied in a multimode microwave cavity at 2.4 GHz. The highest microwave heating rate in the temperature range of 315-355 K was observed in the film close to the critical grain size.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

Effect of precursor on the performance of alumina for the dehydration of methanol to dimethyl ether

Dimethyl ether (DME) is amongst one of the most promising alternative, renewable and clean fuels being considered as a future energy carrier. In this study, the comparative catalytic performance of γ-Al2O3 prepared from two common precursors (aluminum nitrate (AN) and aluminum chloride (AC)) is presented. The impact of calcination temperature was evaluated in order to optimize both the precursor and pre-treatment conditions for the production of DME from methanol in a fixed bed reactor. The catalysts were characterized by TGA, XRD, BET and TPD-pyridine. Under reaction conditions where the temperature ranged from 180 °C to 300 °C with a WHSV = 12.1 h−1 it was found that all the catalysts prepared from AN(η-Al2O3) showed higher activity, at all calcination temperatures, than those prepared from AC(γ-Al2O3). In this study the optimum catalyst was produced from AN and calcined at 550 °C. This catalyst showed a high degree of stability and had double the activity of the commercial γ-Al2O3 or 87% of the activity of commercial ZSM-5(80) at 250 °C.

Acidic properties of nanolayered ZSM-5 zeolites

The acidic properties of nanolayered ZSM-5 zeolites synthesized with the aid of multiquaternary ammonium surfactants were investigated in detail. A substantial fraction of Al is present in highly dispersed form at extraframework positions indicative of the defective nature of the calcined nanolayered zeolites. Acidity characterization reveals that the Brønsted acid sites are similar in strength to those in bulk HZSM-5. Nanolayered zeolites contain a higher amount of Brønsted acid sites (BAS) at their external (mesopore) surface. Unilamellar zeolites have a higher concentration of external BA and silanol sites than multilamellar ones. The number of BAS in the nanolayered zeolites is considerably lower than the tetrahedral Al content, the difference increasing with nanolayer thickness. Except for one particular sample (nanolayered ZSM-5 synthesized from COH template), the total turnover of methanol normalized per BAS trends inversely with the concentration of BAS. There is no correlation with the concentration of external BAS. Catalyst deactivation due to coke mainly depends on the BAS concentration. A unilamellar ZSM-5 zeolite prepared using COH displayed substantially improved performance in terms of a much lower rate of coke deactivation in line with earlier data Choi et al. [10]. Since the acidic and textural properties of this zeolite did not differ significantly from the others, it remains to be determined why this zeolite performs so much better. © 2013 Elsevier Ltd. All rights reserved.

Structural and magnetic properties of Ni1-xZnxFe2O4 (x=0, 0.5 and 1) nanopowders prepared by sol-gel method

A series of nanostructured Ni-Zn ferrites Ni1-xZnxFe2O4 (x=0, 0.5 and 1) with a grain size from 24 to 65 nm have been prepared with a sol-gel method. The effect of composition and sintering temperature on morphology, magnetic properties, Curie temperature, specific heating rate at 295 kHz and hysteresis loss have been studied. The highest coercivity of 50 and 40 Oe, were obtained for NiFe2O4 and Ni0.5Zn0.5Fe2O4 samples with the grain size of 35 and 29 nm, respectively. The coercivity of Ni and Ni-Zn mixed ferrites decreased with temperature. The Bloch exponent was 1.5 for all samples. As the grain size increased, the Curie temperature of NiFe2O4 increased from 849 to 859 K. The highest saturation magnetization of 70 emu/g at 298 K and the highest specific heating rate of 1.6 K/s under radiofrequency heating at 295 kHz were observed over NiFe2O4 calcined at 1073 K. Both the magnitude of the hysteresis loss and the temperature dependence of the loss are influenced by the sintering temperature and composition.

Arsenic(III,V) adsorption onto charred dolomite: charring optimization and batch studies

In this work, the removal of arsenic from aqueous solutions onto thermally processed dolomite is investigated. The dolomite was thermally processed (charred) at temperatures of 600, 700 and 800 degrees C for 1, 2, 4 and 8 h. Isotherm experiments were carried out on these samples over a wide pH range. A complete arsenic removal was achieved over the pH range studied when using the 800 degrees C charred dolomite. However, at this temperature, thermal degradation of the dolomite weakens its structure due to the decomposition of the magnesium carbonate, leading to a partial dissolution. For this reason, the dolomitic sorbent chosen for further investigations was the 8 h at 700 degrees C material. Isotherm studies indicated that the Langmuir model was successful in describing the process to a better extent than the Freundlich model for the As(V) adsorption on the selected charred dolomite. However, for the As(III) adsorption, the Freundlich model was more successful in describing the process. The maximum adsorption capacities of charred dolomite for arsenite and arsenate ions are 1.846 and 2.157 mg/g, respectively. It was found that both the pseudo first- and second-order kinetic models are able to describe the experimental data (R-2 > 0.980). The data suggest the charring process allows dissociation of the dolomite to calcium carbonate and magnesium oxide, which accelerates the process of arsenic oxide and arsenic carbonate precipitation. (C) 2014 Elsevier B.V. All rights reserved.

Selection and characterisation of geological materials for use as geopolymer precursors

Geopolymer binders are generally formed by reacting powdered aluminosilicate precursors with alkali silicate activators. Most research to date has concentrated on using either pulverised fuel ash or high purity dehydroxylated kaolin (metakaolin) in association with ground granulated blast furnace slag as the main precursor material. However, recently, attention has turned to alternative calcined clays that are abundant throughout the globe and have lower kaolinite contents than commercially available metakaolins. Due to the lack of clear and simple screening protocols enabling assessment of such geological resources for use as precursors in geopolymer systems, the present paper presents results from experimental work that was carried out to develop a functional binder using materials containing kaolinite taken from the Interbasaltic Formation of Northern Ireland. The influence of mineralogy has been examined, and a screening process, using three Interbasaltic materials as examples, that will assist in the rapid selection of suitable geopolymeric precursors from such materials is outlined.

Effect of type, form, and dosage of activators on strength of alkali-activated natural pozzolans

It is possible to synthesize environmentally friendly cementitious construction materials from alkali-activated natural pozzolans. The effect of the alkaline medium on the strength of alkali-activated natural pozzolans has been investigated and characterised. This paper highlights the effect of the type and form of the alkaline activator, the dosage of alkali and the SiO2/Na2O ratio (silica modulus, Ms) when using water–glass solutions and different curing conditions on the geopolymerisation of natural pozzolans. Activation of natural and calcined pozzolan for production of geopolymeric binder was verified by using Taftan andesite and Shahindej dacite from Iran as a solid precursor. The optimum range for each factor is suggested based on the different effects they have on compressive strength. The concentration of dissolving silicon, aluminium and calcium in alkaline solution, the formation of gel phase and the factors affecting this have been studied by using leaching tests, ICP–AES, and FTIR.

Engineering properties of alkali-activated natural pozzolan concrete

The development of alkali-activated binders with superior engineering properties and longer durability has emerged as an alternative to ordinary portland cement (OPC). It is possible to use alkali-activated natural pozzolans to prepare environmentally friendly geopolymer cement leading to the concept of sustainable development. This paper presents a summary of an experimental work that was conducted to determine mechanical strength, modulus of elasticity, ultrasonic pulse velocity, and shrinkage of different concrete mixtures prepared with alkali-activated Iranian natural pozzolans—namely Taftan andesite and Shahindej dacite, both with and without calcining. Test data were used for Taftan pozzolan to identify the effects of water-binder ratios (w/b) and curing conditions on the properties of the geopolymer concrete, whereas the influence of material composition was studied by activating Shahindej pozzolan both in the natural and calcined states. The results show that alkali-activated natural pozzolan (AANP) concretes develop moderate-to-high mechanical strength with a high modulus of elasticity and a shrinkage much lower than with OPC.

Effect of adding mineral additives to alkali-activated natural pozzolan paste

Natural pozzolans are raw materials from geological deposits with a range of chemical compositions that when combined with suitable alkali activators can be converted to geopolymer cement for concrete production. In this paper the concept of adding mineral additives to enhance the properties of geopolymer cement is introduced. Taftan andesite, a natural Iranian pozzolan, was used to study the effect of adding mineral additives such as kaolinite, lime and other calcined pozzolans on the compressive strength of geopolymer cement under both normal and autoclave curing. Scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) was used to determine the composition of the gel phase in both alkali-activated Taftan pozzolan with and without mineral additions. The work has shown that deficiencies in SiO2, Al2O3 and CaO content in the raw natural pozzolan can be compensated for by adding mineral additives for enhanced properties.

Effect of heat treatment on reactivity-strength of alkali-activated natural pozzolans

Natural pozzolans can be activated and condensed with sodium silicate in an alkaline environment to synthesize high performance cementitious construction materials with low environmental impact. The nature of the starting materials including mineral composition, chemical composition and crystal structure groups affects the formation of the geopolymer gel phase. In this paper, the pozzolanic activities of five natural pozzolans are studied. From XRD and XRF results, most of the raw materials contain zeolite clay minerals and have a high loss on ignition. Therefore, before use, samples were calcined at 700, 800 and 900 °C, respectively. The improvement in pozzolanic properties was studied following heat treatment including calcinations and/or elevated curing temperature by using alkali solubility and compressive strength tests. The results show that pozzolan containing sodium zeolite clinoptilolite can be used to prepare a moderate to high strength binder by heat treatment and calcinations can impart disorder hornblende as a constituent of pozzolan with no amorphous phase to prepare a moderate strength binder.