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.     

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.     

Acid-enhanced limestone defluoridation in column reactor using oxalic acid

Acid enhanced limestone defluoridation of water has been studied in a crushed limestone column reactor using oxalic acid (OA). The defluoridation has been studied with varying initial fluoride concentrations of 5, 10, 15 and 20 mg/L and acid concentrations of 0.01, 0.05 and 0.1 M. The fluoride removal was found to increase with increase in the concentration of the acid, removing fluoride up to 95% with 0.1 M OA. The observed good fluoride removal has been attributed to a combination of two mechanisms of fluoride removal, viz., precipitation of calcium fluoride and adsorption of fluoride ions on limestone surfaces. While the removal by precipitation remains same on repeated use of the same limestone column, the adsorption is more with the fresh limestone and decreases gradually on repeated use of the same limestone column. The precipitate has been characterized using various analytical tools, viz., X-ray diffraction, IR spectroscopy, thermogravimetric analysis, scanning electron microscopy combined with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The Ca²⁺ ions, formed due to dissolution of limestone by the acid, precipitate calcium fluoride along with precipitation of calcium oxalate. A good fluoride removal ability, low residual oxalate, acceptable final pH, low-cost and simplicity of the process make the present acid-enhanced limestone defluoridation process with OA a potential method for defluoridation of groundwater.     

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.     

Drop in dry mass and organic substance content in the process of autothermal thermophilic aerobic digestion

This paper presents the results of a study of a sludge subjected to the (ATAD) process – Autothermal Thermophilic Aerobic Digestion occurring in a two-stage installation operated in a municipal wastewater treatment plant in Olecko, Poland. The study of the sludge and the analysis of obtained results were conducted over 2011 and 2014. The subject of the study was a thickened sludge in an intermediate tank from which it was next transferred to facility reactors. The stabilization of processed sludge was evaluated analyzing the change in the dry mass (DS) content in the sludge. Measurements were carried out in thickened sludge samples and after the ATAD process. Collected results were then subjected to a statistical analysis and it was determined to which extent as resulted from the subject process the dry mass and the dry organic mass (VS) content was changing in the sludge. Also, it was analyzed how the oxygen chemical demand (COD) was changing. The dry mass content in the thickened sludge was from 60 g/l to 160 g/l. After the process, this amount was from 35 to 76 g/l. Similarly, the organic mass content in a dry sludge mass changed from initial values within a range of 44–135 g/l to 23–60 g/l after the ATAD process. Also, the organic substance content expressed as COD decreased from 80 to 467 g O₂/l in a thickened sludge to 51–261 g O₂/l in the sludge after the process. The article presents conclusions from the result of the conducted study as well as personal experience.     

Detoxification of hexavalent chromium in wastewater containing organic substances using simonkolleite-TiO2 photocatalyst

Innovative simple method for the preparation of simonkolleite-TiO₂ photocatalyst with different Zn contents was achieved. The prepared photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, Raman and diffuse reflectance spectroscopy techniques. The photocatalytic activities of the materials were evaluated for the simultaneous detoxification of hexavalent chromium (Cr(VI)) and oxidation of organic compounds commonly present in wastewater under simulated solar light. The best photoreduction efficiency of Cr(VI) has been achieved at 1000 ppm simonkolleite-TiO₂ photocatalyst of 5% Zn/TiO₂ weight ratio, and pH value of 2.5 to enhance the adsorption onto catalyst surface. Photoreduction was significantly improved by using formic acid as holes scavenger owing to its chemical adsorption on the catalyst surface. Finally, 100% photoreduction of Cr(VI) could be achieved using formic/simonkolleite-TiO₂ systems under sunlight.     

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.     

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.     

Methane–air mixtures ignited by CW laser-heated targets on optical fiber tips: Comparison of targets,optical fibers,and ignition delays

Fiber optic systems are being deployed in locations where explosive gas atmospheres are normally present or are present under fault conditions. The National Institute for Occupational Safety and Health, Pittsburgh Research Laboratory (NIOSH, PRL) conducted a study of laser safety in potentially flammable environments. Researchers conducted experiments to estimate the mean and standard deviation of laser powers needed to ignite 6% methane–air atmospheres using single mode optical fiber tips covered by two types of iron oxide (Fe₃O₄ and (FeMn)₂O₃) mixed with a ceramic adhesive. The iron oxides, heated by a 1064 nm continuous wave laser, ignited the methane–air mixtures at similar powers. The minimum igniting power and maximum non-igniting power (10 tests) were 407 and 350 mW, respectively, using a 62.5 μm fiber. Laser beams guided by 125 and 80 μm diameter cladding single mode fibers produced similar methane–air igniting powers. Ignition was not observed using coal particles at powers that produced ignition with the iron oxides. Threshold ignition delays using the single mode fiber were approximately proportional to the inverse square of the igniting power. Ignition delays were significantly longer than the reported activation time for a commercial fiber optic power limiter. Comparisons are made with the results of other researchers.     

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.     

Synthesis of CuO nanoparticles through green route using Citrus limon juice and its application as nanosorbent for Cr(VI) remediation: Process optimization with RSM and ANN-GA based model

In present investigation, an attempt has been made for the synthesis of cupric oxide nanoparticles (CuONPs) through a green route by utilizing lemon juice extract as a bioreductant. The synthesized CuONPs were characterized through UV–visible spectroscopy, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The CuONPs were utilized for Cr(VI) removal from water through adsorption method in batch mode at different initial Cr(VI) concentration, pH, temperature and CuONPs dosage. The maximum uptake capacity of CuONPs was found to be 16.63 mg of Cr(VI)/g at pH 4.0. Implementation of response surface methodology (RSM) followed by artificial neural network hybridized with genetic algorithm (ANN-GA) approach has resulted maximum Cr(VI) adsorption of 98.8% under the optimized conditions of initial metal concentration 22.5 mg/L, pH 3.81, CuONPs dose 1.28 g/L and temperature 37.1 °C. Under optimum conditions, adsorption isotherm study was conducted, which showed that the fitness of experimental data was well achieved with Langmuir isotherm model illustrating monolayer pattern of adsorption. Thermodynamic study revealed that the process was spontaneous and endothermic in nature, while adsorption kinetics was best explained by pseudo-second order kinetic model.     

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.     

Enhanced NOx removal from flue gas by an integrated process of chemical absorption coupled with two-stage biological reduction using immobilized microorganisms

An integrated process of metal chelate absorption coupled with two stage bio-reduction using immobilized cultures has been proposed to continuously removal of NO_x, and the effects of SO₂, NO and O₂ concentration, gas/liquid flow rate on NO_x removal efficiency were investigated. Although nitrogen-containing components, such as Fe(II)EDTA-NO, NO₂^? and NO₃^? in the scrubbing solution, inhibited the bio-reduction of Fe(III)EDTA obviously, it was feasible to abate the inhibition effect by using the two stage bio-reduction system, and thus to improve NO_x removal efficiency. The removal efficiency decreased slowly with the increase of SO₂, O₂, NO concentration and gas flow rate, and increased with the increase of liquid flow rate. Continuously operating for 18 days, a high removal efficiency around 95% was reached by using the two-stage bio-reduction system with immobilized microorganisms, while the value decreased to 85% after 5 days of operation by using the suspended microorganisms, at a constant gas flow rate of 60 L/h containing 424–450 mg/m³ NO, 2428–2532 mg/m³ SO₂ and 3% O₂.     

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.     

Investigation on removal of p-nitrophenol using a hybridized photo-thermal activated persulfate process: Central composite design modeling

The aim of this work is the study of p-nitrophenol (PNP) removal, as a nitroaromatic compound, using a hybridized photo-thermally activated potassium persulfate (KPS) in a fully recycled batch reactor. Response surface method was used for modeling the process. Reaction temperature, KPS initial dosage and initial pH of the solution were selected as variables, besides PNP degradation efficiency was selected as the response. ANOVA analysis reveals that a second order polynomial model with F-value of 41.7, p-value of 0.0001 and regression coefficient of 0.95 is able to predict the response. Based on the model, the process optimum conditions were introduced as initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 66 °C. Also experiments showed that using thermolysis and photolysis of the persulfate simultaneously, the role of thermolysis is not considerable. A pseudo first order kinetic model was established to describe the degradation reaction. Operational cost, as a vital industrial criterion, was estimated so that the condition of initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 25 °C showed the highest cost effective case. Under the preferred mild condition, the process will reach to 84% and 89% of degradation and mineralization efficiencies, after 60 and 120 min, respectively.     

Experimental investigation of the flow characteristics of jettisoning in a CO2 carrier

This experimental study was performed to investigate the flow characteristics in the jettisoning flow line of a liquid CO₂ carrier. When a pressurized liquid CO₂ container loses mechanical integrity, possibly by material or mechanical defects, the liquid inventory should be drained out rapidly for safety reasons using the so-called jettisoning process. In the course of jettisoning, the liquid CO₂ undergoes two phase change stages, from liquid to liquid + vapor and from liquid + vapor to solid + vapor. Consequently, the jettisoning release rate is affected by the characteristics of these phase changes. In this study, liquid CO₂ was discharged through a small tube, representing a jettisoning flow line. The temperature and pressure were measured along the tube, and the locations of the phase changes were inferred from the measured data. The experimental results showed that active nucleation occurred near the tube tip and that the phase change into solid and vapor occurred just after leaving the pipe, irrespective of the tube length in this study.     

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.     

Characterization of heavy metals in fly ash from municipal solid waste incinerators in Shanghai

This study aims to develop a methodology for analysis of characteristics of heavy metals in MSWI fly ash. It performed analysis of composition of heavy metals, leaching toxicity, leaching behavior as a function of pH, specification distribution and corresponding mineral components of residue derived from each step of the sequential extraction. It is found that content of heavy metals follows the sequence of Zn > Pb > Cu > Cr > As > Ni > Cd approximately Hg in both plants, and that total heavy metals account for less than 1% by mass of fly ash. Major hazardous heavy metals in fly ash are As, Cd, Hg, Pb and Zn, whose leaching ratios exceed the limit value described in hazardous waste identification standard. Measured leaching results of Cu, Pb and Zn are essentially consistent with the simulated results at pH between 0 and 13. Content of calcium-silicates, alumino-silicates and glass phases in residue derived from sequential extraction procedure increases steadily from the first step to the fifth step of the sequential extraction procedure. Cu, As, Cr, Hg, Cd, and Ni, relatively stable under strong basic conditions, can be leached out under strong acidic conditions, while Zn and Pb tend to be leached out under both strong acidic and basic conditions.     

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.     

Removal of humic substances from landfill leachate by Fenton oxidation and coagulation

In this study, chemical oxygen demand (COD) was characterized as total organic constituents and the isolated humic substances (HS) were characterized as an individual organic contaminant in landfill leachate. It was found that the HS content of landfill leachate was 83.3%. The results of laboratory tests to determine the roles of HS in reducing the organic content of landfill leachate during Fenton process are presented. Furthermore, the performances of oxidation and coagulation of Fenton reaction on the removal of HS and COD from leachate were investigated. The change curves of HS removal were similar to those of COD. The HS removal was 30% higher than COD removal, which indicated that HS were mostly degraded into various intermediate organic compounds but not mineralized by Fenton reagent. The oxidation removal was greatly influenced by initial pH relative to the coagulation removal. The oxidation and coagulation removals were linear dependent with hydrogen peroxide and ferrous dosages, respectively. Ferrous dosage greatly influenced the coagulation removal of COD at low ratio ([H₂O₂]/[Fe²⁺] < 3.0), but not at extremely high ratio ([H₂O₂]/[Fe²⁺] > 6.0). The coagulation removal of HS was not affected obviously by oxidation due to both Fenton oxidation and coagulation remove high molecular weight organics preferentially. Higher temperature gave a positive effect on oxidation removal at low Fe²⁺ dosage, but this effect was not obvious at high Fe²⁺ dosage.