An Experimental Study on Pyrolysis of Biomass

In this study, pyrolysis of sugarcane bagasse was performed in fixed bed tubular reactor under the conditions of nitrogen atmosphere, by varying temperature and different particle sizes. The effect of final pyrolysis temperature from 400 to 500°C and the nitrogen flow rate from 50 to 200 cc min⁻¹ on the pyrolysis product yields from sugarcane bagasse have been investigated. The Maximum bio-oil yield obtained is 24.12 wt% at the final pyrolysis temperature of 450°C, N₂ flow rate of 50 cc min⁻¹ and particle size of mesh number −8 + 12. The yield of bio-oil decreases with increase in temperature from 450 to 550°C and N₂ flow rate from 50 to 200 cc min⁻¹. The various characteristics of pyrolysis oil obtained under these conditions were identified on the basis of standard test methods. The empirical formula of pyrolysis oil with a heating value of 37.01 MJ Kg⁻¹ was established as CH_1.434 O_0.555 N_0.004. The results from the pyrolysis show the potential of sugarcane bagasse as an important source of liquid hydrocarbon fuel.     

Recycling of valuable chemicals through the catalytic decomposition of phenol tar in cumene process

The base catalyst LZ-2, which was the mixture of CaO and Na–NaOH/Al₂O₃·3H₂O, was chosen for the decomposition of phenol tar to generate valuable chemicals. The selectivity of LZ-2 for dimethyl phenyl carbinol, α-methyl styrene dimer and cumenyl phenol was 100%, 100% and 98%, respectively. Under the optimum operating conditions of catalyst 2.5 wt%, operating temperature 603.15 K and decomposition time 3.5 h, decomposition ratios of cumenyl phenol and dimethyl phenyl carbinol were 98.7% and 99.97%, respectively. In addition, the experimental repeatability demonstrated that the total yield of valuable chemicals still reached 90.1% after the catalyst being used five times. Mass and energy balance indicated that the catalytic decomposition was a high potential for the recycling of chemicals from phenol tar.     

Thermal characterization of fly ash from one municipal solid waste incinerator (MSWI) in Shanghai

This study aims to develop a methodology for the thermal characterization of MSWI fly ash. We performed TGA–DTA and component variation analysis, microstructure transfer of sintered fly ash, as well as leaching toxicity, volatilization ratio and specification transformation of heavy metals as a function of temperature. It is found that content of crystal phases first increases between room temperature and 800 °C and then decreases between 800 °C and 1200 °C, while that of glass phases registers a reverse trend. Fly ash registers a SiO₂–Al₂O₃–metal oxides system and its content of glass phases is around 57%. Increase of sintering temperature between 600 °C and 1200 °C is conducive to the reduction of soluble As, Cd, Cu, Hg, Pb, Ni and Zn, while content of soluble Cr increases as temperature rises from 800 °C to 1200 °C.     

Experimental study of the characteristics of solid fuel from fry-dried swine excreta

Swine excreta were dried by boiling via immersion in hot oil. In this method, moisture in the excreta is replaced with oil or evaporated by turbulent heat transfer in high-temperature oil. The dried excreta can be used in an incinerator like low-rank coal or solid fuel. Refined waste oil and B–C heavy oil were used for drying. Drying for 8 min at 150 °C reduced the water content of raw excreta from 78.90 wt.% to 1.56 wt.% (refined waste oil) or 1.62 wt.% (B–C heavy oil) and that of digested excreta from 79.58 wt.% to 3.40 wt.% (refined waste oil) or 3.48 wt.% (B–C heavy oil). The low heating values of the raw and digested excreta were 422 kJ/kg and ?2,713 kJ/kg, respectively, before drying and 27,842–28,169 kJ/kg and 14,394–14,905 kJ/kg, respectively, after drying. A heavy metal analysis did not detect Hg, Pb, Cd, As, and Cr in the dried excreta, but Al, Cu, and Zn, which occur in the feed formula, were detected. Thermogravimetric analysis before and after drying revealed that emission of volatiles and combustion of volatiles and fixed carbon occurred at temperatures of 250–500 °C when air was used as the transfer gas.     

Growing Carbon Nanotube on Aluminum Oxides: An Inherently Safe Approach for Environmental Applications

Using micron-sized Al₂O₃ particles as carriers to grow carbon nanotubes (CNTs) under 700°C atmosphere of methane and hydrogen after pre-planted catalysts of Fe–Ni nanoparticles, those composite CNTs (CCNTs) have demonstrated several unique properties compared to CNTs—medium specific surface area and zeta potential, high adsorption capacity for metal ions, high recovery rate by acids, low decomposition heat for exothermal reaction, and so on. The adsorption behaviours of Pb²⁺, Cu²⁺ and Cd²⁺ in aqueous solutions by CCNTs are in good agreement with the Langmuir adsorption isotherm and second order kinetic model with maximum individual adsorption capacities of 67.11, 26.59 and 8.89 mg g⁻¹. The individual and competitive adsorption behaviours indicated that the preference order of adsorption were Pb²⁺ > Cu²⁺ > Cd²⁺ for aluminum oxides, activated carbon, commercial CNTs, and CCNTs as well as other researchers’ CNTs. We suggest that future development of CNTs to combine with metals and/or other materials, such as TiO₂, should consider attached to carriers or surface in order to avoid concerns on environment, health and safety. Thus, growing CNTs on Al₂O₃ particles to form CCNTs is an inherently safe approach for many promising environmental applications.     

Effect of ultrasound irradiation and Ni-loading on properties and performance of CeO2-doped Ni/clinoptilolite nanocatalyst used in polluted air treatment

In this research nanocatalysts containing 5, 10 and 15 wt.% of Ni, dispersed by sonication over CeO₂–clinoptilolite composite support were compared toward total oxidation of toluene. Their catalytic performance at different temperatures between 150 and 350 °C was studied based on the oxidative destruction of toluene. The results indicated that the activity of Ni/CeO₂–clinoptilolite nanocatalyst for toluene oxidation increased from 33 to 44% at 250 °C by employing sonochemical method in synthesis of catalyst. Meanwhile, the catalytic activity was also improved when Ni content was increased from 5 to 10 and 15 wt.%. With the aid of several characterization techniques like XRD, FESEM, PSD, EDX, BET and FTIR, the correlation between nanocatalyst structure and its activity was addressed. It is indicated that sonochemical method can lift the catalytic activity due to the better dispersion of catalyst active components and also higher surface area. Among sonicated samples, 15 wt.% Ni nanocatalyst showed the highest toluene oxidation due to the better dispersion of catalyst active components and hence to more effective catalytic sites.     

Evaluation of beech for production of bio-char,bio-oil and gaseous materials

Evaluation of Oriental beech (Fagus orientalis L.) was investigated with aspect of thermo-chemical conversion to obtain bio-char, bio-oil and gaseous. When the pyrolysis temperature increased, the bio-char yield decreased. A high temperature and smaller particles increase the heating rate resulting in a decreased bio-char yield. The bio-char obtained are carbon rich, with high heating value and relatively pollution-free potential solid biofuel. The liquefaction yield sharply increased with increasing the temperature near critical temperature and after that. In the pyrolysis, increases of liquid yields are considerably sharply for all of the samples with increasing of pyrolysis temperature from 690 K to 720 K. The beechnut oil was converted to biodiesel in supercritical methanol without using the catalyst. Experiments have been carried out in an autoclave at 493, 523 and 593 K, and with molar ratios of 1:6–1:40 of the oil to methanol. The yield of alkyl ester increased with increasing the molar ratio of oil to alcohol.     

Optimization of novel pyrazolium ionic liquid catalysts for transesterification of bitter apple oil

In the present study, 4 different functionalized pyrazoliums based on sulfoalkyl-pyrazolium hydrogensulfate and alkylsulfo-alakylpyrazolium hydrogensulfate were explored to catalyze biodiesel production from bitter apple oil (BAO). The results demonstrated that a longer chains catalyst of 2-(4-sulfobutyl) pyrazolium hydrogensulfate (SBPHSO₄) exhibited the highest catalytic activity, which is attributed to its strong acidity. The highest yield of esters was up to 89.5% when the reaction was carried out under the conditions of 5.2 wt% of SBPHSO₄, molar ratio of methanol to BAO of 15:1, 170 °C, and 800 rpm for 6 h. These results demonstrated that ionic liquids offer a promising new type of pyrazolium catalyst for biodiesel production. The use of clean ionic liquids in preparing clean biodiesel could solve the drawbacks associated with using the old conventional catalysts and might be employed as an efficient catalyst for such relevance.     

Preparation of Co–MgO mixed oxide nanocatalysts for low temperature CO oxidation: Optimization of preparation conditions

In this study, a series of Co–MgO mixed oxides (30 wt.% Co) were prepared by co-precipitation method and employed as catalyst in low temperature CO oxidation reaction. The preparation conditions were optimized by the Taguchi method of experimental design to synthesize a sample with high catalytic performance toward CO oxidation reaction. The effects of four variables, pH of solution, aging temperature, aging time and molarity of precursor solution at three levels were investigated. The optimized sample was characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of oxygen (O₂-TPD), N₂ adsorption/desorption, thermal gravimetric and differential thermal analysis (TGA/DTA), and transmission electron microscopy (TEM) techniques. The results revealed that the optimized sample showed a mesoporous structure with a narrow pore size distribution centered in the range of 7–17 nm and particle size about 5.5 nm. It was found that the molarity of solution and aging time had the most influence on the CO conversion, respectively. The catalytic results showed that the highest CO conversion obtained from samples synthesized by Taguchi orthogonal array was about 90% at 200 °C, while the CO conversion for optimized sample was 95%. In addition, the effect of operational conditions was studied over optimized sample.     

Refinery wastewater degradation with titanium dioxide,zinc oxide,and hydrogen peroxide in a photocatalytic reactor

This paper presents the photo-catalytic degradation of real refinery wastewater from National Refinery Limited (NRL) in Karachi, Pakistan, using TiO₂, ZnO, and H₂O₂. The pretreatment of the refinery effluent was carried out on site and pretreated samples were tested at 32–37 °C in a stirrer bath reactor by using ultra-violet photo oxidation process. The degradation of wastewater was measured as a change in initial chemical oxygen demand (COD) and with time. Optimal conditions were obtained for catalyst type, and pH. The titanium dioxide proved to be very effective catalysts in photo-catalytic degradation of real refinery wastewater. The maximum degradation achieved was 40.68% by using TiO₂ at 37 °C and pH of 4, within 120 min of irradiations. When TiO₂ was combined with H₂O₂ the degradation decreased to 25.35%. A higher reaction rate was found for titanium dioxide. The results indicate that for real refinery wastewater, TiO₂ is comparatively more effective than ZnO and H₂O₂. The experiments indicated that first-order kinetics can successfully describe the photo-catalytic reaction. The ANOVA results for the model showed satisfactory and reasonable adjustment of the second-order regression model with the experimental data. The ANOVA results also showed that pH is significant than reaction time and catalyst dosage of TiO₂; and in case of ZnO, reaction time is significant than pH and catalyst dosage. This study proves that real refinery wastewater reacts differently than synthetic refinery wastewater, oil field produced water or oil water industrial effluent.     

An explosion of a tank car carrying waste hydrogen peroxide

On the Metropolitan Expressway in Tokyo, a tank car exploded because it was carrying hydrogen peroxide (H₂O₂) in a compartment in which copper chloride (CuCl₂) remained. Although the main cause of the accident was trivial, the background on the accident suggested that an induction period in the reaction led to a mistake. This report describes the experimental investigation of the catalytic ability of CuCl₂, and comparing it with two other copper(II) compounds (nitrate: Cu(NO₃)₂; and copper sulfate: CuSO₄) and three iron(III) compounds (chloride: FeCl₃; nitrate: Fe(NO₃)₃; and sulfate: Fe₂(SO₄)₃).The experiments were performed using a reaction calorimeter. During the experiments at 35 °C, 2×10⁻⁵ mol of copper compounds slowly reacted with H₂O₂ and generated a precipitate. The iron compounds allowed the hydrogen peroxide to violently decompose. A 1×10⁻⁴ mol solution of CuCl₂, however, produced a violent decomposition at 35 °C. At 15 °C, a moderate heat release occurred.Based on these results, the concentration and temperature dependence of the catalytic ability of CuCl₂ were postulated to contribute to the induction period observed in the accident.     

7 mT static magnetic exposure enhanced synthesis of poly-3-hydroxybutyrate by activated sludge at low temperature and high acetate concentration

The effect of 7 mT (milliTesla) SMF (static magnetic field) on poly-3-hydroxybutyrate (PHB) production was studied at an acetate concentration of 260 Cmmol l^?1 and temperature of 10 °C. The SMF decreased the specific acetate uptake rate by 29%, but increased the maximum PHB content and the yield of PHB on acetate by 32 and 28% respectively. The ratio q_P/(q_S ? q_P), which described specific PHB production rate over the difference between specific acetate uptake rate and specific PHB production rate, was introduced for evaluation of the ratio of carbon flux into PHB synthesis and into the TCA (tricarboxylic acid) cycle. This value reached 2.3 when activated sludge culture was exposed to magnetic field of 7 mT, which was 1.1 times higher than the q_P/(q_S ? q_P) value obtained without magnetic exposure. Therefore, the SMF promoted diversion of more acetyl-CoA towards PHB synthesis and could offset adverse effects of high acetate concentration and low temperature. These results provide evidence that SMF enhances PHB production by activated sludge.     

Synthesis of Bio-Diesel and Bio-Lubricant by Transesterification of Vegetable Oil with Lower and Higher Alcohols Over Heteropolyacids Supported by Clay (K-10)

The use of different lower and higher alcohols viz; methanol, ethanol, n-propanol and n-octanol, for the synthesis of methyl, ethyl, propyl and octyl fatty acid esters by transesterification of vegetable oil (triglycerides) with respective alcohols also known as ‘Bio-diesel’ and ‘Bio-lubricants’ was studied in detail. The reactions were carried out in a batch process. The activity with different supports like clay (K-10), activated carbon, ZSM-5, H-beta and TS-1 were compared. The superacids (heteropolyacids, HPA) viz; Dodeca-Tungstophosphoric acid [H₃PO₄·12 WO₃·xH₂O] (TPA) and Dodeca-Molybdo phosphoric acid ammonium salt hydrate [H₁₂Mo₁₂N_3-O₄₀P + aq] (DMAA) was used to increase the acidity and so the activity by loading on the most active support viz; clay (K-10). These HPA loaded on clay as a catalyst was used for the following study: effect of percent HPA loading on clay, effect of different vegetable oils, effect of different alcohols on the triglyceride conversion based on glycerol formation and selectivity based on alkyl esters formation. The data is compared at the best-optimized identical set of operating reaction conditions: 170 °C, 170 rpm, catalyst loading: 5% (w/w of reaction mixture), molar ratio (oil: alcohol): 1:15 and time on stream of 8 h. The generated data is also evaluated based on the reported one.     

A novel pretreatment process of mature landfill leachate with ultrasonic activated persulfate: Optimization using integrated Taguchi method and response surface methodology

A novel advanced oxidation process (AOP) using ultrasonic activated persulfate oxidation was used to pretreat mature landfill leachate. The effects of different operating variables (e.g., the initial S₂O₈²⁻ concentration, pH, temperature, ultrasonic power and reaction time) on the oxidation performance were investigated regarding the total organic carbon (TOC) removal efficiency, and the variables were optimized using the integrated Taguchi method and response surface methodology (RSM). Based on the Taguchi method under L₁₆ (4⁵) arrays and a grey relational analysis, the most significant variables included the initial S₂O₈²⁻ concentration, temperature and reaction time. The concentrations of these variables were further optimized using RSM. Using the integrated optimization method, the optimal conditions included an initial S₂O₈²⁻ concentration of 8.5 mM, a reaction temperature of 70 °C and a reaction time of 2.46 h, which resulted in a TOC removal efficiency of 77.32%. The experimental results showed that the enhanced TOC removal from mature landfill leachate by sono-activated persulfate oxidation could be attributed to the combined effects of ultrasonic catalysis and sulfate radical-AOP. Overall, ultrasonic activated persulfate oxidation is a promising method for the pretreatment of landfill leachate.     

Liquefaction of sawdust in hot compressed ethanol for the production of bio-oils

Direct liquefaction of lignocellulosic waste (sawdust) has been conducted in hot-compressed ethanol at temperatures from 150 to 250 °C. It was found that polyols such as glycerol, glycol and polyethylene glycol (PEG) promoted liquefaction process assisted with hot ethanol treatments seemed promising for production of bio-oils from lignocellulosic materials. Effects of different solvents and catalysts on liquefaction of sawdust were investigated. The results showed that the optimum operating condition for catalytic liquefaction is at 250 °C, 1 h of reaction time using glycerol and ethanol as solvent where operating at this condition realized the highest conversion of sawdust which is 97.8%. After reaction, the liquified product was separated by vacuum distillation. Two fractions were obtained, namely light oil and heavy oil. The properties and compositions of these two fractions were characterized in terms of Fourier transform infrared spectroscopy (FT-IR), gas chromatography–mass spectrometry (GC–MS), size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR).     

Disintegration of waste activated sludge by different applications of Fenton process

Oxidative disintegration of municipal waste activated sludge (WAS) using conventional Fenton (Fe²⁺ + H₂O₂, CFP) and Fenton type (Fe⁰ + H₂O₂, FTP) processes was investigated and compared in terms of the efficiency of sludge disintegration and enhancement of anaerobic biodegradability. The influences of different operational variables namely sludge pH, initial concentration of Fe²⁺ or Fe⁰, and H₂O₂ were studied in detail. The optimum conditions have been found as catalyst iron dosage = 4 g/kg TS, H₂O₂ dosage = 40 g/kg TS and pH = 3 within 1 h oxidation period for both CFP and FTP. Kinetics studies were performed under optimal conditions. It was determined that the sludge disintegration was happened in two stages by both processes: rapid and subsequent slow disintegration stages and rapid sludge disintegration stage can be described by a zero-order kinetic model. The effects of oxidative sludge disintegration under the optimum conditions on anaerobic digestion were experienced with biochemical methane potential (BMP) assay in batch anaerobic reactors. Total methane production in the CFP and FTP pre-treated reactors increased by 26.9% and 38.0%, relative to the untreated reactor (digested the raw WAS). Furthermore, the total chemical oxygen demand reductions in the pre-treated reactors were improved as well.     

Biomass to Fuels: Upgrading of Flash Pyrolysis Oil by Reactive Distillation Using a High Boiling Alcohol and Acid Catalysts

We here report our studies on the upgrading of flash pyrolysis oil using an improved alcohol treatment method. The method consists of treating pyrolysis oil with a high boiling alcohol like n-butanol in the presence of a (solid) acid catalyst at 323–353 K under reduced pressure (<10 kPa). Using this approach, the water content of the pyrolysis oil is reduced significantly. Variables like the type of alcohol (n-butanol, ethylene glycol, 2-ethyl-hexyl-alcohol) and liquid and solid acids were explored and the product properties of the resulting upgraded pyrolysis oil (kinematics viscosity, water content, pH and heating value) were determined. On the basis of these screenings studies, n-butanol and the solid acid Nafion SAC13 seem to have the highest potential. The product properties of the upgraded pyrolysis oils, and particularly the heating value and the acidity are considerably improved. These improvements are not only due to blending effects but also the result of the occurrence of chemical reactions (a.o. esterification).     

Evaluation of Eremurus spectabilis for production of bio-oils with supercritical solvents

Eremurus spectabilis samples were liquefied in organic solvents (methanol, ethanol and acetone) with (sodium hydroxide and ferric chloride) and without catalyst in a cylindrical reactor at temperatures of 270, 290 and 310 °C under supercritical conditions. The effects of liquefaction parameters such as temperature, catalyst and solvent on product yields were investigated. The liquid products were extracted with diethyl ether and benzene using an extraction procedure. The product yields in supercritical methanol, ethanol and acetone were found to as 41.6%, 53.8% and 64.3% in the non-catalytic runs at 310 °C, respectively. The highest conversion was obtained in supercritical acetone in the presence of ferric chloride (10%) at same temperature in the catalytic runs. The produced liquids in acetone were analyzed and characterized by elemental, Fourier transform infrared spectroscopy (FT-IR), gas chromatography–mass spectrometry (GC–MS). The liquid products (bio-oils) obtained with acetone contained various types of components including aromatics, nitrogenated and oxygenated compounds. As the bio-oils obtained exhibit high heat values, E. spectabilis is presented as a potential feedstock candidate for production of bio-fuels or valuable chemicals.     

Mesoporous simonkolleite–TiO2 nanostructured composite for simultaneous photocatalytic hydrogen production and dye decontamination

In the present work, mesoporous simonkolleite–TiO₂ composite was prepared with sol–gel method. The composite photocatalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), and Raman spectroscopy. Also, surface area and particle size were analyzed using BET equation. The photocatalytic hydrogen production with simultaneous decolorization of Remazole Red (F3B) dye was investigated over TiO₂ and simonkolleite–TiO₂ composite under UV–vis light irradiation. It was worthy to be noted that the rate of hydrogen production over simonkolleite–TiO₂ is higher that produced over TiO₂. The maximum amount of photocatalytic-produced hydrogen was 2.1 mmol and 3.3 mmol within 240 min using TiO₂ and simonkolleite–TiO₂ composite, respectively. The specific production rate of hydrogen from photocatalytic conversion of dye was calculated. Improvement of apparent quantum yield (22.07%) after 5 h was achieved upon addition of simonkolleite to TiO₂. This high apparent quantum yield proves that the system proposed in this study could be a hopeful approach toward using sunlight energy as outlook energy source. The obtained results suggested that a new process for H₂ production from wastewater could be achieved. The process also provides a method for degradation of organic pollutants with simultaneous H₂ production.     

Optimizing the preparation parameters of mesoporous nanocrystalline titania and its photocatalytic activity in water: Physical properties and growth mechanisms

Titania nanomaterial with an anatase structure and 5.6 nm crystallite size and 280.7 m² g⁻¹ specific surface areas had been successfully prepared by sol–gel/hydrothermal route. The effect of pH as a type of autoclave and calcination was studied. Crystallite size and phase composition of the prepared samples were identified. X-ray diffraction analyses showed the presence of anatase with little or no rutile phases. The crystallite size of the prepared TiO₂ with acidic catalyst was both smaller than that prepared with basic catalyst, and was increasing after acidic calcinations by a factor 4–5. Basic calcinations produced a specific increase of 1.5. Rutile ratio and the particle size were increased after calcination at 500 °C. However, TiO₂ powder synthesized using a basic catalyst persisted the anatase phase and a loosely aggregation of particles. Anatase TiO₂ as prepared with acidic catalyst in Teflon lined stainless steel autoclave demonstrated the highest photocatalytic activity for degradation of 2,6-dichlorophenol-indophenol under ultraviolet irradiation with t_½ 0.8 min.