Halil Durak

Effects of catalysts and solvents on liquefaction of Onopordum heteracanthum for production of bio-oils.

Milled Onopordum heteracanthum stalks were converted to liquid products in organic solvents (methanol, ethanol and acetone) with (KOH and ZnCl₂) and without catalyst in an autoclave at temperatures of 523, 543 and 563 K. Effects of liquefaction parameters such as catalyst and solvent were investigated. The percentage yields from supercritical methanol, ethanol and acetone conversions were 48.2, 50.4 and 66.2 at 563 K in the non-catalytic runs, respectively. In the catalytic run with ZnCl₂, the highest conversion (70.2%) was obtained in acetone at the same temperature. The obtained liquid products at 563 K were analyzed and characterized by elemental, Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry. 106 different compounds have been identified by GC-MS in the liquid products obtained in methanol at 563 K.

Hydroxyapatite-nanosphere supported ruthenium(0) nanoparticle catalyst for hydrogen generation from ammonia-borane solution: kinetic studies for nanoparticle formation and hydrogen evolution

The development of readily prepared effective heterogeneous catalysts for hydrogen generation from ammonia-borane (AB; NH3BH3) solution under mild conditions still remains a challenge in the field of “hydrogen economy”. In this study, we report our finding of an in situ generated, highly active ruthenium nanocatalyst for the dehydrogenation of ammonia-borane in water at room temperature. The new catalyst system consists of ruthenium(0) nanoparticles supported on nanohydroxyapatite (RuNPs@nano-HAp), and can be reproducibly prepared under in situ conditions from the ammonia-borane reduction of Ru3+ ions exchanged into nanohydroxyapatite (Ru3+@nano-HAp) during the hydrolytic dehydrogenation of ammonia-borane at 25 ± 0.1 °C. Nanohydroxyapatite-supported ruthenium(0) nanoparticles were characterized by a combination of advanced analytical techniques. The sum of their results shows the formation of well-dispersed ruthenium(0) nanoparticles with a mean diameter of 2.6 ± 0.6 nm on the surface of the nanospheres of hydroxyapatite by keeping the host matrix intact. The resulting RuNPs@nano-HAp are highly active catalyst in the hydrolytic dehydrogenation of ammonia-borane with an initial TOF value of 205 min−1 by generating 3.0 equiv. of H2 per mole of ammonia-borane at 25 ± 0.1 °C. Moreover, they are sufficiently stable to be isolated and bottled as solid materials, which can be reused as active catalyst under the identical conditions of first run. The work reported here also includes the following results: (i) monitoring the formation kinetics of the in situ generated RuNPs@nano-HAp by hydrogen generation from the hydrolytic dehydrogenation of ammonia-borane as the reporter reaction. The sigmoidal kinetics of catalyst formation and concomitant dehydrogenation fits well to the two-step, slow nucleation, followed by autocatalytic surface growth mechanism, P → Q (rate constant k1) and P + Q → 2Q (rate constant k2), in which P is Ru3+@nano-HAp and Q is the growing, catalytically active RuNPs@nano-HAp; (ii) the compilation of kinetic data for the RuNPs@nano-HAp catalyzed hydrolytic dehydrogenation of ammonia-borane depending on the temperature and catalyst concentration to determine the dependency of reaction rate on catalyst concentration and activation parameters (Ea, ΔH#, and ΔS#) of the reaction.

Bio-oil production via catalytic pyrolysis of Anchusa azurea: Effects of operating conditions on product yields and chromatographic characterization.

Pyrolysis of Anchusa azurea, a lignocellulosic gramineous plant, was carried out in a tubular, fixed-bed reactor in the presence of four catalysts (Ca(OH)2, Na2CO3, ZnCl2, Al2O3). The influences of pyrolysis parameters such as catalyst and temperature on the yields of products were studied. It was found that higher temperature resulted in lower liquid (bio-oil) and solid (bio-char) yields and higher gas yields. Catalysts effected the yields of products differently and the composition of bio-oils. Liquid yields were increased in the presence of Na2CO3, ZnCl2 and Al2O3 and decreased with Ca(OH)2. The highest bio-oil yield (34.05%) by weight including aqueous phase was produced with Na2CO3 catalyst at 450°C. The yields of products (bio-char, bio-oil and gas) and the compositions of the resulting bio-oils were determined by GC-MS, FT-IR and elemental analysis. GC-MS identified 124 and 164 different compounds in the bio-oils obtained at 350 and 550°C respectively.

Optimization of the Dissolution of Tincal Ore in Phosphoric Acid Solutions at High Temperatures

The aim of the study was to investigate the optimization of the dissolution of tincal ore in phosphoric acid solutions at high temperatures in a batch reactor. The effect of the following parameters on the dissolution process was investigated: the reaction temperature, the phosphoric acid concentration, the particle size, and the solid-to-liquid ratio. The best conditions for the dissolution were determined using the 24 factorial experimental design method. The optimum values of the parameters were experimentally determined. The effective parameters were the reaction temperature, the phosphoric acid concentration, the particle size, and the solid-to-liquid ratio. The optimum conditions resulted in the maximum boron dissolution at an acid concentration of 1 M, reaction temperature of 85°C, particle size of 4.75 mesh, and solid-to-liquid ratio of 1/6 g · mL−1. Under these optimum conditions, the best dissolution yield was 98.26%.

Pyrolysis of Xanthium strumarium in a fixed bed reactor: Effects of boron catalysts and pyrolysis parameters on product yields and character

ABSTRACT Pyrolysis of Xanthium strumarium has been performed in a fixed-bed tubular reactor with boron minerals (ulexite, colemanite, and borax) and without catalyst at three different temperatures ranging from 350°C to 550°C with heating rate of 50°C/min. The amounts of bio-oil, bio-char, and gas generated, also the compositions of the resulting bio-oils were identified by GC-MS and FT-IR. The influences of pyrolysis parameters, such as temperature and catalyst on product yields were investigated. Temperature and catalyst were found to be the main factors affecting the conversion of Xanthium strumarium into solid, liquid, and gaseous products. The highest liquid yield (27.97%) including water was obtained with 10% colemanite (Ca2B6O11.5H2O) catalyst at 550°C temperature at a heating rate of 50°C/min when 0.224 > Dp > 0.150 mm particle size raw material and 100 cm3/min of sweeping gas flow rate were used.

Pyrolysis of giant mullein (Verbascum thapsus L.) in a fixed-bed reactor: Effects of pyrolysis parameters on product yields and character

ABSTRACT Slow pyrolysis of giant mullein (Verbascum thapsus L.) stalks have been carried out in a fixed-bed tubular reactor with (Al2O3, ZnO) and without catalyst at four different temperatures between 400 to 550°C with a constant heating rate of 50°C/min and with a constant sweeping gas (N2) flow rate of 100 cm3/min. The amounts of bio-char, bio-oil, and gas produced were calculated and the compositions of the obtained bio-oils were determined by gas chromatography-mass spectrometry. The effects of pyrolysis parameters, such as temperature and catalyst, on the product yields were investigated. The results show that both temperature and catalyst have significant effects on the conversion of Verbascum thapsus L. into solid, liquid, and gaseous products. The highest liquid yield of 40.43% by weight including the aqeous phase was obtained with 10% zinc oxide catalyst at 500°C temperature. Sixty-seven different products were identified by gas chromatography-mass spectrometry in the bio-oils obtained at 500°C temperature.

Catalytic effects of borax and iron(III) chloride on supercritical liquefaction of Anchusa azurea with methanol and isopropanol

ABSTRACT Anchusa azurea is a lignocellulosic gramineous plant, and it has been selected as a renewable feedstock to be used in a liquefaction process to obtain biofuel. Milled Anchusa azurea stalks were converted to liquid products in methanol and isopropanol with (borax or iron(III) chloride) and without catalyst in an autoclave at temperatures of 260, 280, and 300°C. The liquefaction parameter effects such as catalyst, solvents, and temperature were investigated. The highest percentages of liquid yields from methanol and isopropanol conversions were 64.70% (with borax) and 29.20% (with borax) at 300°C in the catalytic runs, respectively. The highest conversion (73.80%) was obtained in methanol with borax catalyst at the same temperature. The obtained liquid products at 300°C were analyzed and characterized by elemental, Fourier transform infrared spectroscopy and gas chromatography–mass spectrometry (GC-MS). Seventy-three different compounds have been identified by GC-MS in the liquid products obtained in methanol at 300°C.