Use of advance oxidation process to improve the biodegradability of olive oil mill effluents

In this study, recalcitrant total phenol (TPh) and organic matter removal were investigated at olive mill wastewater (OMW) in sequential Coagulation and Fenton system. This study focused on different operational parameters such as pH, H₂O₂, and Fe²⁺ dosages, and [Fe²⁺]/[H₂O₂] ratios. The optimum conditions were determined as; pH = 3; [Fe²⁺] = 2.5 g/L; [Fe²⁺]/[H₂O₂] = 2.5. A higher treatment efficiency was achieved at sequential Coagulation and Fenton system (COD, 65.5%) and TPh, 87.2%), compared to coagulation process (COD, 51.4%; total organic carbon (TOC), 38.6% and total nitrogen (TN) 52.1%). This study demonstrated that the Coagulation and Fenton process has a potential for efficient removal of phenolic pollutants from wastewater.     

The effects of activated Al2O3 on the recycling of light oil from the catalytic pyrolysis of waste printed circuit boards

The effects of employing activated Al₂O₃ during the catalytic pyrolysis of waste printed circuit boards (WPCBs) are investigated, focusing on the recycling of light oil. Variations in the pyrolysis process are studied through analysis of the phase distribution, water content and boiling point fractions of the resulting products. Product composition and carbon number distribution are analyzed using gas chromatography techniques. The use of activated Al₂O₃ increases the light oil fraction and also reduces the quantity of brominated products formed. It was determined that the best yield of light oil and most efficient debromination resulted from catalytic pyrolysis at 600 °C. Applying catalyst-to-feed ratios in the range of 1.0–1.5 also maximizes the yield of light oil. The major oil fraction resulting from catalytic pyrolysis has a boiling point range of 0–250 °C and carbon number range of C6–C9, showing for use as a potential fuel after suitable treatment such as hydrogenation. At a higher catalyst-to-feed ratio of 2.0, activated Al₂O₃ generates a high proportion of light oil fractions containing a significant quantity of chemicals such as phenol (52.67% at 600 °C), although an overall lower yield of oil is obtained. The oil produced in this manner may also be used as a raw material feedstock for the production of various other useful chemicals.     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

Inherently safer reactors: Improved efficiency of 3-picoline N-oxidation in the temperature range 110–125 °C

Alkylpyridine N-oxides are important intermediates in the pharmaceutical and agrochemicals industries. The N-oxides are produced via the homogeneously catalyzed oxidation of the respective alkylpyridines using a 50% excess of hydrogen peroxide. The competitive hydrogen peroxide decomposition produces oxygen in the flammable environment of alkylpyridines and thus forms a key hazard for this reaction. In this work, the N-oxidation was performed under pressure in the temperature range of 110–125 °C with different catalyst concentrations. It was shown that temperature had an undisputable positive effect on the N-oxidation efficiency. The accurate measurement of the pressure rise due to decomposition was difficult. However, only 5% of the added H₂O₂ decomposed when stoichiometric quantities were employed, even in the temperature of 110 °C. The N-oxidation was very efficient, even when the lowest concentration of catalyst employed in this study was used.     

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.     

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.     

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.     

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.     

Calorimetric behaviors of N2H4 by DSC and superCRC

The objective of this study is to obtain information about the thermal decomposition behaviors of hydrazine (N₂H₄) caused by metals, using differential scanning calorimeter (DSC) and SuperCRC. The DSC measurements revealed that the exothermic reactions of N₂H₄ were caused by the reaction conditions such as the type of cells; the T_DSC with a gold pan is 485.2 K and that with a glass capillary is 620.5 K. Besides, the activation energy of the thermal decomposition of N₂H₄, calculated from the Kissinger and Ozawa methods, were found to be about 38±2 kJ mol⁻¹ in the gold pan and 141±8 kJ mol⁻¹ in the glass capillary. Moreover, a heat flow profile was observed with SuperCRC during the mixing of N₂H₄ and the metal ion solution at 298 K. The maximum heat flow was related to the metal ion oxidative characters. The higher oxidative characters would provide a faster acceleration for the exothermic behavior than the lower oxidative ions. Based on this study, Mn(VII) and Cr(VI) were considered to exhibit strongly oxidative characteristics during mixing with N₂H₄.     

Simultaneous photocatalytic treatment of Cr(VI), Ni(II) and SDBS in aqueous solutions: Evaluation of removal efficiency and energy consumption

Simultaneous photocatalytic reduction of poisonous Cr(VI) and Ni(II) ions, coupled with photocatalytic oxidation of sodium dodecyl benzene sulfonate (SDBS) were studied with a trace amount of commercial titania nanoparticles and by means of a direct-photo-irradiation reactor. The co-presence of metal ions and SDBS causes metal ions reduction as well as SDBS oxidation to enhance and energy efficiency to improve. XRD, XPS and FTIR analysis were used to characterize TiO₂ particles before and after usage with the aim of evaluating the mechanism of reactions. The effect of major operating parameters, pH and temperature, was investigated. Under conditions of [Cr(VI)]₀ = [Ni(II)]₀ = 5 mg/L, [SDBS]₀ = 10 mg/L, [TiO₂] = 40 mg/L, pH 6 and T = 35 °C; the removal efficiencies of 55.4%, 71.2% and 57.2% were obtained, respectively, for Cr(VI) and Ni(II) reduction, as well as for SDBS oxidation, after 110 min operation. The relevant kinetic model jointed with the Arrhenius equation was introduced. Pseudo-first-order reactions are relevant. Energy consumption (electrical and thermal) evaluations revealed that operations at higher temperatures provide significant cost reduction. Meantime, a criterion was proposed for a consistent assessment of this kind of processes.     

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.     

Pretreatment of municipal landfill leachate by a combined process

Biodegradability enhancement of landfill leachate using air stripping followed by coagulation/ultrafiltration (UF) processes was introduced. The air stripping process obtained a removal efficiency of 88.6% for ammonia nitrogen (NH₄–N) at air-to-liquid ratio of 3500 (pH 11) for stripping 18 h. The single coagulation process increased BOD/COD ratio by 0.089 with the FeCl₃ dosage of 570 mg l^?1 at pH 7.0, and the single UF process increased the BOD/COD ratio to 0.311 from 0.049. However, the combined process of coagulation/UF increased the BOD/COD ratio from 0.049 to 0.43, and the final biological oxygen demand (BOD), chemical oxygen demand (COD), NH₄–N and colour of leachate were 1223.6 mg l^?1, 2845.5 mg l^?1, 145.1 mg l^?1 and 2056.8, respectively, when 3 kDa molecular weight cut-off (MWCO) membrane was used at the operating pressure 0.7 MPa. In ultrafiltration process, the average solution flux (J_V), concentration multiple (M_C) and retention rate (R) for COD was 107.3 l m^?2 h^?1, 6.3% and 84.2%, respectively.     

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.     

Effects of applied voltage on hydrogen production rate of a single reactor BML with Clostridium sp.

This study aimed to explore the influences of single-chamber systems with different applied voltage on bio-hydrogen (H₂) production. The reactor used was the bio-electrochemically assisted microbial reactor (BEAMR) membrane-less (BEAMR-membrane-less, BML). The microbial dark fermentative H₂ production method was adopted. After the hot screening process and the DNA sequencing, the domesticated dominant microflora was Clostridium sp. This study discussed the influences of the cases with (continuous and intermittent) and without applied voltage separately. The results showed that, the H₂ production rate of the case with intermittent applied voltage (117 mL/h g VSS) of 0.24 V was increased of 1.7 folds higher than the without applied voltage (69 mL/h g VSS) and 1.3 folds higher than the case with continuous applied voltage (88.2 mL/h g VSS) of 0.24 V. The produced H₂ concentration with intermittent applied voltage was 18.9% (18.6–19.1%) higher than the without applied voltage, while there was no significant difference with continuous applied voltage.     

Comparative response of two organic biofilters treating ethylbenzene and toluene after prolonged exposure

The response of two biofilters filled with an organic waste material for treating ethylbenzene and toluene was studied for 415 and 472 operating days, respectively. The peak elimination capacities (EC_MAX) recorded were 170 g m^?3 h^?1 for ethylbenzene (EC_MAX) and 138 g m^?3 h^?1 for toluene. Regarding the degradation profile through the biofilters, an increase in the inlet concentration displaced the degradation profile into the downstream section. A sudden decrease in the performance of both biofilters occurred when the moisture content (MC) of the packing material exceeded 37% for ethylbenzene and 30% for toluene. Thus, a recommended MC value was established in the 15–30% range. Given the bioreactor was operated at a low MC level, fungi prevailed over bacteria. Nevertheless, synergism was detected between both microorganism types for the mineralization of the aromatic hydrocarbons.     

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 improved method of removal for high concentrations of NO by electro-scrubbing process

In the Ag(II)/Ag(I) redox mediator integrated scrubber system, NO reacts with the Ag(II) ions produced by the electrochemical oxidation of Ag(I) in an electrochemical cell present in the scrubbing solution (aqueous HNO₃ acid) to form NO₂. This NO₂ is then absorbed into the scrubbing solution and degraded to nitrate. Numerous experimental runs were carried out to evaluate the feasibility of the integrated system to treat industrial waste gases containing high NO_x levels. The results showed that the levels of NO and NO_x removal increased with increasing Ag(II) loading and contact time. Under optimized conditions, 93.5% and 73.3% of the NO and NO_x, respectively, were removed by a single stage gas scrubber with 1.62 g L^?1 Ag(II) operating at 25 °C and atmospheric pressure.     

Removal of H2S by co-immobilized bacteria and fungi biocatalysts in a bio-trickling filter

Biological control of odor gases has gained more attention in recent years. In this study, removal performance of a vertical bio-trickling filter inoculated with bacteria and fungi was studied. Bacteria and fungi were isolated from activated sludge in a sewage treatment plant. By adopting “three step immobilization method”, the bio-trickling filter could degrade pollutant immediately once hydrogen sulfide (H₂S) passed. The optimal empty bed resident time was 20 s. The optimal elimination capacity was about 60 g H₂S m^?3 h^?1 with removal efficiency of 95%. And the maximum elimination capacity was 170 g H₂S m^?3 h^?1. Pressure drop was ranged between 5 and 15 mm H₂O per bed over the whole operation. Removal efficiency was not affected obviously after terminating nutrient supply. The bio-trickling filter could recover back after shut down H₂S gaseous and liquid supplies simultaneously. Microbial community structure in the bio-trickling filter was not changed significantly.Combining bacteria and fungi would be a better choice for inoculation into a bio-trickling filter because of the quickly degradation of H₂S and rapid recovery under shut-down experiment. This is the first study attempting to combine bacteria and fungi for removal of H₂S in a bio-trickling filter.     

Decolorization of synthetic Methyl Orange wastewater by electrocoagulation with periodic reversal of electrodes and optimization by RSM

Treatment of Methyl Orange (MO), an azo dye, synthetic wastewater by electrocoagulation with periodic reversal of the electrodes (PREC) was examined. Response Surface Methodology (RSM) was used to optimize the influence of experimental conditions for color removal (CR), energy consumption (ENC), electrode consumption (ELC) and sludge production (SP) per kg MO removed (kg(MO_r)) with optimal conditions being found to be pH 7.4, solution conductivity (к) 9.4 mS cm⁻¹, cell voltage (U) 4.4 V, current density (j) 185 mA cm⁻², electrocoagulation time (T) 14 min, cycle of periodic reversal of electrodes (t) 15 s, inter-electrode distance (d) 3.5 cm and initial MO concentration of 125 mg L⁻¹. Under these conditions, 97 ± 2% color was removed and ENC, ELC and SP were 44 ± 3 kWh kg(MO_r)⁻¹, 4.1 ± 0.2 kg(Al) kg(MO_r)⁻¹ and 17.2 ± 0.9 kg(sludge) kg(MO_r)⁻¹, respectively. With the enhanced electrochemical efficiency resulting from the periodic electrode reversal, the coefficients of increased resistance and decreased current density between the two electrodes in the PREC setup were 2.48 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.29 mA cm⁻² min⁻¹, respectively, as compared to 7.72 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.79 mA cm⁻² min⁻¹ as measured for the traditional electrocoagulation process. The rate constant of decolorization was also enhanced by 20.4% from 0.152 min⁻¹ in the traditional electrocoagulation process to 0.183 min⁻¹ in the PREC process. These performance characteristics indicate that the PREC approach may be more promising in terms of practical application, as a cost-effective treatment, than conventional electrocoagulation for textile dye removals.     

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.