Dilute Acid Hydrolysis of Cellulose and Cellulosic Bio-Waste Using a Microwave Reactor System

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175°C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175°C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k₁ = 0.0813 s⁻¹; k₂ = 0.0075 s⁻¹, which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent ‘hot spot’ formation within the reactor, which would have cause localised degradation of glucose.     

Disintegration of municipal waste activated sludge by simultaneous combination of acid and ultrasonic pretreatment

The individual and simultaneous effects of acid and ultrasonic pretreatment on the disintegration of municipal waste activated sludge (WAS) were investigated based on chemical properties of WAS. In the combination of acid and ultrasonic pretreatment methods (ultrasonic-acid pretreatment), lowering pH accelerated and enhanced the disintegration of waste biological sludge. Therefore, the same disintegration efficiency (obtained by ultrasonic pretreatment alone) was achieved by the combined pretreatment in shorter sonication times. Optimum pretreatment conditions were ultrasonic power density of 1.0 W/mL and pretreatment time of 10 min for ultrasonic pretreatment alone, and ultrasonic power density of 1.0 W/mL, pretreatment time of 10 min and initial sludge pH of 2.0 for the combined pretreatment. Sludge disintegration degrees were about 30% and 40% under these optimized conditions, respectively. Optimum sludge concentration was found to be 1.0% total solid (TS) content for the combined pretreatment. As a result, ultrasonic-acid pretreatment has been determined as a new and effective combined sludge pretreatment method to improve the sludge disintegration.     

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.     

Improving disintegration and acidification of waste activated sludge by combined alkaline and microwave pretreatment

The individual alkaline or microwave pretreatment has been proved to be effective in disintegration and acidification of waste activated sludge (WAS). In this study, the effects of combined alkaline and microwave pretreatment at different pH and specific energy input (Es) on WAS disintegration were investigated using response surface methodology (RSM). Combined pretreatment achieved disintegration degree (DD) of 65.87% at Es of 38,400 kJ/kg TS and pH 11.0. The ANOVA further demonstrated that pH showed more significant effect on DD than Es. Anaerobic batch experiment results showed that combined pretreatment not only significantly improved volatile fatty acids (VFAs) accumulation but also shortened the time for the highest VFAs accumulation. The maximal VFAs accumulation (1500 mg COD/L) obtained at Es of 28,800 kJ/kg TS and fermentation time of 72 h, which was about two times that of the treatment without microwave (850 mg COD/L) at 96 h. The analysis of VFAs composition showed that the VFAs mainly consisted of acetic and iso-valeric acids, accounting for 57.3–70.1% of total VFAs.     

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.     

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.     

Overall and local movement speeds during fire drill evacuations in buildings up to 31 stories

The time that it takes an occupant population to reach safety when descending a stairwell during building evacuations is typically described by measurable engineering variables such as stairwell geometry, speed, density, and pre-evacuation delay. In turn, engineering models of building evacuation use these variables to predict the performance of egress systems for building design, emergency planning, or event reconstruction. As part of a program to better understand occupant movement and behavior during building emergencies, the Engineering Laboratory at the National Institute of Standards and Technology (NIST) has been collecting stairwell movement data during fire drill evacuations of office buildings. These data collections are intended to provide a better understanding of this principal building egress feature and develop a technical foundation for future codes and standards requirements. To date, NIST has collected fire drill evacuation data in eight office building occupancies ranging from 6 to 62 stories in height that have included a range of stairwell widths and occupant densities.While average movement speeds in the current study of 0.48 m/s ± 0.16 m/s are observed to be quite similar to the range of literature values, local movement speeds as occupants traverse down the stairwell are seen to vary widely within a given stairwell, ranging from 0.056 m/s to 1.7 m/s. These data should provide confirmation of the adequacy of existing literature values typically used for occupant movement speeds or provide updated values for future analyses.     

Boron removal from produced water using electrocoagulation

Produced water is the largest wastestream of oil and gas exploration but its chemical composition hinders its beneficial use. Effective treatment and reuse of produced water can mitigate scarcity of fresh water, especially in arid areas. Presence of inorganic compounds such as boron in produced water renders its beneficial use difficult. In this study, boron removal from produced water was investigated. Synthetic wastewater was prepared simulating the range of boron concentrations in produced water. Four operating parameters pH (3–11), charge loading (1200–3600 Ah/m³), contact time (15–90 min) and concentration (10–30 mg/L) were selected and their optimum conditions investigated. The obtained optimum conditions were applied to treat real produced water. Residual boron concentration of 0.3 mg/L was obtained from initial boron concentration of 15 mg/L in real produced water at optimum conditions of pH 7, charge loading 2400 Ah/m³ and contact time 90 min. Boron adsorption could be represented by Langmuir and Freundlich isotherm models. Electrocoagulation can be used for the effective removal of boron from produced water.     

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.     

Continuous nitrifying granular sludge bioreactor: Influence of aeration and ammonium loading rate

Granulation of nitrifying bacteria was investigated in a continuous bubble column bioreactor. Then, the combined effect of aeration and ammonium loading rates on dissolved oxygen (DO) concentration as well as nitrification process was evaluated in the system using an experimental design technique. After 120 days, stable nitrifying granules with average diameter of 1.4 mm and settling velocities of 55 m/h were obtained. The influence of increasing ammonium loading rate (ALR) was found to be more significant than decreasing aeration rate on the reduction of DO concentration inside the nitrifying bioreactor. The system could handle the ALR values of 0.48–1.92 gNH₄⁺-N/L d with the ammonium removal efficiency from 65% to nearly 100% at the tested airflow rates of 2.5 and 4.5 L/min. At the low aeration, the complete ammonium conversion to nitrate was replaced with nitrite when the ALR increased to 1.44 gNH₄⁺-N/L d. At the high aeration, however, almost complete nitrification was achieved except the high ALR in which the nitrite accumulation was observed up to 38%. The study demonstrated that the continuous bioreactor had a considerable performance for obtaining stable nitrifying granules to have nitrite accumulation under control with changing the ratio of aeration rate and ALR.     

Effects of high ammonia loads on nitrogen mass balance and treatment performance of a biotrickling filter

A biotrickling filter packed with coal slag as packing medium was continuously used for more than 9 months under high ammonia loading rates of up to 140 g/m³/h. Nitrogen mass balance and microbial community analysis were conducted to evaluate the inhibitory effects of high ammonia concentration and metabolic by-products on the rates of nitrification. Ammonia removal efficiency reached above 99% at an empty bed retention time of as low as 8 s when inlet concentrations were below 350 ppm. The maximum and critical elimination capacities of the biotrickling filter were 118 g/m³/h and 108.1 g/m³/h, respectively. Kinetics analysis results showed that less than 2.5 s was required for the biotrickling filter with pH control to treat ammonia at concentrations of up to 500 ppm in compliance with the Taiwan EPA standard (outlet NH₃ < 1 ppm). Results of mass balance and microbial community analysis indicated that complete removal was mainly contributed by the activities of autotrophic ammonia oxidizing bacteria and not by physical absorption or adsorption at low loading rates. However, at high inlet loadings, ammonium became the dominant by-product due to inhibitory effects of high ammonia concentration on the bacterial community.     

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.     

Anaerobic digestion modeling of the main components of organic fraction of municipal solid waste

The organic fraction of municipal solid waste (OFMSW) is composed of several heterogeneous organic and inorganic wastes. The diversity of composition, the high volatile solid content and the biodegradable material that this waste offers make it quite an interesting option for anaerobic digestion (AD). Depending on the substrate composition, the biological degradation and kinetics of the AD could vary. Biochemical methane potential (BMP) tests are used as a tool to evaluate the methane production of several fractions of OFMSW, in order to study the influence of each fraction in the final mixture. The kinetic parameters of methane curves and the prediction of final productions are studied by different approaches to model equations using linear, exponential, logistic and Gaussian models. The analyses of the fractions indicate that organic substrates such as meat/fish which are in a small proportion in the final mixture, obtain major productivities (291 ± 3 mlCH₄/gVS), however others such as paper (217 ± 5 mlCH₄/gVS) could have their productivity enhanced due to their high VS present in the final mixture. Both the Gomperzt and the first order model fit reasonably with all the fractions, although substrates with lag phase adjust only to the Gompertz model explaining 99% of the experimental results.     

Vented confined explosions in Stramberk experimental mine and AutoReaGas simulation

Research Mining Institute, Inc., Ostrava-Radvanice, in cooperation with Dept. of Theory And Technology of Explosives of University of Pardubice and Klokner Institute of CTU in Prague, has performed three series of experiments examining methane–air mixture explosions and their impact on 14 and 29 cm thick wall. The project was named ‘Modeling Pressure Fields Effects on Engineering Structures During Accidental Explosions of Gases in Buildings’ and was sponsored by Grant Agency of Czech Republic (project No. 103/01/0039). The project is aimed at deeper understanding of pressure field effect upon the structures. Methane-air mixture explosion was used to generate the blast wave. The geometrical configuration of the environment resembled a room of an average size, such as larger kitchen. Preliminary simulations were made by AutoReaGas code (Century Dynamics and TNO). The design phase was followed by tests in an experimental mine in Stramberk. Two masonry dams were build in the mine, with cross-section areas of 10.2 m² and longitudinal distance of 5.7 m, creating an explosion chamber with a volume of 58 m³. Two vent openings with an adjustable free cross-section were used to control the maximum overpressure inside the chamber. The concentration of methane-air mixture was approximately 9.5% (vol.) and the volumes of the clouds were 5.25, 10.2 and 15.3 m³ respectively. The generated blast wave overpressures inside the chamber ranged between 1 and 150 kPa. According to experimental results a calibration of the code was performed. After the calibration it is possible to make relatively accurate simulations in similar geometry and to calculate the pressure loading of the structure at any spot in the simulated space. This paper describes the experiments performed and compares experimental and computational results.     

Removal of toluene vapour from air stream using a biofilter packed with polyurethane foam

Biodegradation of toluene vapour was investigated for 168 days in a polyurethane packed biofilter inoculated with a mixed microbial population. Biofilter consisted of five square cross-section modular units each of size 0.16 m × 0.16 m × 0.20 m and filled with the polyurethane foam cubes up to a height of 0.15 m. Inlet concentration of toluene was varied from 0.04 to 2.5 g m^?3 and the volumetric flow rate of toluene loaded air from 0.06 to 0.90 m³ h^?1.Depending upon initial loading rates, removal efficiency ranging from 68.2 to 99.9% and elimination capacity ranging from 10.85 to 90.48 g h^?1 m^?3 were observed during steady state operations. More than 90% removal efficiency was observed up to an inlet loading rate of 76.3 g h^?1 m^?3. High carbon recovery (>90%) indicated effective biodegradation in the bed. Low variation of pH (7.2–8.8) and pressure drop (45.8–76.3 Pa) was observed. The stability of the biomass was evident from the fast response of the biofilter to shutdown and restartup.     

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.     

Partial nitritation of landfill leachate with varying influent composition under intermittent aeration conditions

The start-up and operation of a partial nitritation sequencing batch reactor for the treatment of landfill leachate were carried out on intermittent aeration mode. Partial nitrite accumulation was established in 15 days after the mode was changed from continuous aeration to intermittent aeration. Despite the varying influent composition, partial nitritation could be maintained by adjusting the hydraulic retention time (HRT) and the air flow rate. An increase in the air flow rate together with a decrease in air off duration can improve the partial nitritation capacity and eventually result in the development of granular sludge with fine diameters. A nitrogen loading rate of 0.71 ± 0.14 kg/m³/d and a COD removal rate of 2.21 ± 0.13 kg/m³/d were achieved under the conditions of an air flow rate of 19.36 ± 1.71 m³ air/m³/h and an air on/off duration of 1.5 min/0.7 min. When the ratio of total air flux (TAF) to the influent loading rate (ILR) was controlled at the range of 163–256 m³ air/kg COD, a stable effluent NO₃^?–N/NO_x^?–N (NO₂^?–N plus NO₃^?–N) ratio below 13% was achieved. Interestingly, the effluent pH was found to be a good indicator of the effluent NO₂^?–N/NH₄⁺–N ratio, which is an essential parameter for a subsequent anaerobic ammonium oxidation (Anammox) reactor.     

Investigation of affecting parameters on treating high-strength compost leachate in a hybrid EGSB and fixed-bed reactor followed by electrocoagulation–flotation process

In this research, treatability of high-load compost leachate in a hybrid expanded granular sludge bed (EGSB) and fixed-bed (FB) bioreactor followed by electrocoagulation–flotation (ECF) system was examined. The operational factors in EGSB–FB were influent chemical oxygen demand (COD), hydraulic retention time (HRT) and COD/nitrogen ratio (COD/N). And, their interactive effects on the efficiency of COD removal and biogas production rate (BPR) as responses were analyzed and correlated by response surface methodology (RSM). The optimum conditions of the hybrid EGSB–FB reactor were acquired at COD = 7800 mg/L, HRT = 35 h, COD/N = 70, in which COD removal efficiency was 83% and BPR 94 mL/h. The amount of confidence interval was 95%. COD (relevant coefficient = 9.8) and HRT (relevant coefficient = −24) were resulted respectively as the most effective parameters on COD removal and BPR. Yet, COD/N parameter imposed negative effect on COD removal and BPR in values less than about 100. The outcomes indicated that operated ECF as post-treatment in constant conditions (electrolysis time = 75 min, electrodes distance = 3 cm, voltage = 20 V) successfully satisfied discharge criteria in the most part of experimental domains.     

Coupling of polyhydroxyalkanoate production with volatile fatty acid from food wastes and excess sludge

In this paper, the synthesis of polyhydroxyalkanoates (PHAs) by activated sludge with aerobic dynamic feeding process was conducted in a sequencing batch reactor by using food wastes and excess sludge fermentation liquid as the carbon source. The volatile fatty acids (VFAs) in the fermentation liquid were divided into even-numbered (acetic and butyric acid) and odd-numbered (propionic and valeric acid). The experiments conducted by central-composite design (CCD) showed that the pH could significantly affect the ratio of even-numbered to odd-numbered VFAs. Statistical analysis indicated a positive correlation (R² = 0.97, P < 0.05) between the consumption of even-numbered VFAs and the synthesized of PHB, while the consumption of odd-numbered VFAs were correlated with the synthesized PHV. By controlling the ratio of even-numbered to odd-numbered VFAs, the contents of PHV in the PHAs could be controlled within the range of 22–30%. When fermentative VFAs were used as the substrate for the synthesis of PHAs, the microbial synthesis of PHA and biomass was higher than that mixture of analytically pure acids was used. These results are of vital significance for the comprehensive utilization of solid wastes.     

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.