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.     

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.     

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.     

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.     

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.     

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 biodiesel production from the waste cooking oil using response surface methodology

In this research, transesterification of the waste cooking oil has been studied. Response surface methodology (RSM) based on Box–Behnken design was used to investigate the effects of the main operating parameters, including the methanol to oil molar ratio, catalyst concentration, and reaction temperature, on the biodiesel yield. The results revealed that the catalyst concentration is the most important parameter. The maximum biodiesel yield under the optimized conditions was 99.38 wt.%. Thermogravimetric analysis (TGA) was used for the determination of biodiesel conversion and the results were compared with that of gas chromatography (GC) analysis, showing a very small difference. Furthermore, an empirical quadratic equation has been presented to show the relation between biodiesel conversion and product viscosity.     

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.     

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.     

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.     

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.     

Artificial neural network modelling of As(III) removal from water by novel hybrid material

The present study reported a method for removal of As(III) from water solution by a novel hybrid material (Ce-HAHCl). The hybrid material was synthesized by sol–gel method and was characterized by XRD, FTIR, SEM–EDS and TGA–DTA. Batch adsorption experiments were conducted as a function of different variables like adsorbent dose, pH, contact time, agitation speed, initial concentration and temperature. The experimental studies revealed that maximum removal percentage is 98.85 at optimum condition: pH = 5.0, agitation speed = 180 rpm, temperature = 60 °C and contact time = 80 min using 9 g L⁻¹ of adsorbent dose for initial As(III) concentration of 10 mg L⁻¹. Using adsorbent dose of 10 g L⁻¹, the maximum removal percentage remains same with initial As(III) concentration of 25 mg L⁻¹ (or 50 mg L⁻¹). The maximum adsorption capacity of the material is found to be 182.6 mg g⁻¹. Subsequently, the experimental results are used for developing a valid model based on back propagation (BP) learning algorithm with artificial neural networking (BP-ANN) for prediction of removal efficiency. The adequacy of the model (BP-ANN) is checked by value of the absolute relative percentage error (0.293) and correlation coefficient (R² = 0.975). Comparison of experimental and predictive model results show that the model can predict the adsorption efficiency with acceptable accuracy.     

Kinetic analysis of transesterification of waste pig fat in supercritical alcohols

The kinetic analysis method using non-isothermal technique was proposed to determine the kinetic parameters for the transesterification reaction of waste pig fat in supercritical alcohols. To investigate the transesterification of waste pig fat, the waste pig fat to alcohol ratio (w/w) was varied from 1:1.5 to 1:2.5 between the temperatures 220 and 290 °C at an interval of 10 °C in a 25 mL batch reactor. The products were analyzed by gas chromatography mass spectrometry. To verify the effectiveness of the proposed kinetic analysis method, the experimental values were compared with the values calculated using the kinetic parameters obtained from this work. It was found that the proposed kinetic analysis method gave reliable kinetic parameters for the transesterification of waste pig fat in supercritical alcohols. Further, it was found that the apparent activation energy for supercritical ethanol was lower than the value for supercritical methanol.     

Effect of solvent on the hydrothermal liquefaction of macro algae Ulva fasciata

Hydrothermal liquefaction is an attractive approach for the conversion of aquatic biomass like algae as it does not require the energy intensive drying steps. The objective of the study is to understand the effect of various solvents (H₂O, CH₃OH and C₂H₅OH) on product distribution and nature of products of hydrothermal liquefaction of macro algae Ulva fasciata (MAUF). Hydrothermal liquefaction of MAUF was performed using subcritical H₂O (300 °C) as well as supercritical organic solvents CH₃OH and C₂H₅OH (300 °C). The use of alcoholic solvents significantly increased the bio-oil yield. The bio-oil yield was 44% and 40% in case of liquefaction with CH₃OH and C₂H₅OH respectively whereas the bio-oil yield was 11% with H₂O. Use of alcoholic solvents converted the acids obtained in bio-oil to the corresponding methyl and ethyl esters. ¹H NMR data showed that use of alcoholic solvents (C₂H₅OH and CH₃OH) increased aliphatic content of bio-oil1 (ether/methanol/ethanol fraction). FTIR and SEM results showed the difference in the bio residue obtained using alcoholic solvents and H₂O. The results showed that liquefaction with supercritical alcohols is an effective way to produce functional hydrocarbons for chemical feedstock.     

Effect of spark duration on explosion parameters of methane/air mixtures in closed vessels

The paper outlines an experimental study on influence of the spark duration and the vessel volume on explosion parameters of premixed methane–air mixtures in the closed explosion vessels. The main findings from these experiments are: For the weaker ignition the spark durations in the range from 6.5 μs to 40.6 μs had little impact on explosion parameters for premixed methane–air mixtures in the 5 L vessel or 20 L vessel; For the same ignitions and volume fractions of methane in air the explosion pressures and the flame temperatures in both vessels of 5 L and 20 L were approximately the same, but the rates of pressure rises in both vessels of 5 L and 20 L were different; The explosion indexes obtained from the measured pressure time histories for both vessels of 5 L and 20 L were approximately equal; For the weaker ignition with the fixed spark duration 45 μs the ignition energies in the range from 54 mJ to 430 mJ had little impact on the explosion parameters; For the same ignition and the volume fractions of methane in air, the vessel volumes had a significant impact on the flame temperatures near the vessel wall; The flame temperatures near the vessel wall decreased as the vessel volumes increased.     

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.     

Pb(II) adsorption from aqueous solutions by raw and treated biomass of maize stover – A comparative study

The potential to remove Pb(II) ion from wastewater treatment systems using raw and treated maize stover through adsorption was investigated in batch experiments. To achieve this, batch mode experiments were conducted choosing specific parameters such as pH (2–8), dosage concentration (2–30 g L⁻¹), contact time (5–180 min), temperature (20–45 °C) and metal ion concentrations (10–50 mg L⁻¹). Adsorption was pH-dependent showing a maximum at pH value 5. The equilibrium sorption capacities of raw and treated maize stover were 19.65 and 27.10 mg g⁻¹, respectively. The adsorption data fitted well to the Langmuir isotherm model. Kinetic studies revealed that the adsorption process followed pseudo-second-order model. The calculated thermodynamic parameters showed that the adsorption of Pb(II) was spontaneous and exothermic in nature. Consequently, this study demonstrated that both raw and treated maize stover could be used as adsorbents for the treatment of Pb(II) from industrial wastewaters.     

Dehydration of ethanol with different salts in a packed distillation column

This work aimed the evaluation of a saline extractive distillation for the ethanol production. A thermodynamic model was used to predict the influence of the salts in the liquid–vapor equilibrium of the system water–ethanol and inside the packed column. The experiments were done in a distillation unit, with an internal diameter of 5.9 cm and a packing section with 37 cm of height, packed with raschig rings with 0.73 cm of characteristic inner made of glass. All the bottom and top samples were analyzed by refractive index. Two synthetic charges with the same composition of ethanol that are produced in the refinery (0.02 and 0.25 mol.L^-1) were distilled under atmospheric pressure. Sodium chloride, calcium chloride, potassium acetate, calcium nitrate and a mixture of sodium and potassium acetates were added to the synthetic charges and the results were compared to the experiments already done without the presence of the salts, revealing the ethanol enrichment in the top product of the distillation unit, for all the systems analyzed. Another charge from the refinery, known as load of wine without yeast, was evaluated and the results indicated the same behavior, enriching the ethanol with the application of the saline extractive distillation.     

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.     

Biohydrogen production using waste activated sludge as a substrate from fructose-processing wastewater treatment

Biohydrogen production by dark fermentation in a series of batch tests under different environmental control conditions was evaluated to determine the optimal initial cultivation pH and temperature for a continuous-flow kinetic test to validate the kinetic model system. The waste activated sludge (WAS) from fructose-processing manufacturing was used as the model substrate for biohydrogen production. The batch experiments for biohydrogen production were conducted in a 6 l bioreactor. Fifteen batch kinetic tests were investigated when pH was controlled at 6, 7, 8 and 9 as well as the temperature was controlled at 37 °C, 45 °C and 55 °C, respectively. The experimental results indicated that the optimal operational condition for hydrogen production occurred while pH was 7 and temperature was 55 °C with the highest hydrogen production of 7.8 mmol. The optimal recovery time for hydrogen was 25 h in the batch experiments. Furthermore, the kinetic test of biohydrogen production was performed by anaerobic mixed microbial culture in the continuous-flow experiment when pH and temperature was maintained at 7 and 55 °C. Approximately 60% and 7% of substrate solution was converted into acetate and hydrogen, respectively, at the steady state. Roughly only 0.77% and 2.7% of substrate solution was converted into propionate and butyrate, respectively, at a steady-state condition. The experimental and modeling approaches presented in this study could be employed for the design of pilot-scale and full-scale anaerobic biohydrogen fermentors using food-processing waste activated sludge (WAS) as a substrate solution.