Photochemical Degradation of Aqueous Polyvinyl Alcohol in a Continuous UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Process: Experimental and Statistical Analysis

Polyvinyl alcohol (PVA), being a dominant contributor of total organic carbon (TOC) in textile wastewater, is not easily degradable by conventional methods of wastewater treatment. This study investigates the degradation of aqueous PVA in a continuous UV/H₂O₂ photoreactor since the feeding strategy of hydrogen peroxide proves to have considerable effects on the process performance. Response surface methodology involving the Box–Behnken method is adopted for the experimental design to study the effects of operating parameters on the process performance. Experimental analysis shows that the TOC removal varies from 16.11 to 42.70 % along with a reduction of the PVA molecular weights from 56.7 to 95.3 %. The TOC removal is significantly lower than the molecular weight reduction due to the generation of the intermediate products during oxidation. Operating the UV/H₂O₂ process in a continuous mode facilitates the degradation of highly concentrated polymeric solutions using a relatively small hydrogen peroxide concentration in the feed with a small residence time ranges from 6.13 to 18.4 min.     

Effect of ZnCl<Subscript>2</Subscript> impregnation ratio on pore structure of activated carbons prepared from cattle manure compost: application of N<Subscript>2</Subscript> adsorption-desorption isotherms

Activated carbons were prepared from cattle manure compost (CMC) by ZnCl₂ activation with various ZnCl₂/CMC mass ratios. Based on the N₂ adsorption-desorption isotherms, mathematical models including the Dubinin-Radushkevich (DR) equation, the α_s plot, and the Horvath-Kawazoe method were used to analyze the pore structural characteristics of the prepared activated carbons. It was found that for carbons possessing both micro-and mesopores, the DR method provided a more accurate estimation than the α_s method for the extent of microporosity. The effect of the ZnCl₂ impregnation ratio on the pore structure was discussed using the DR method. The results revealed that pore evolution involved three distinct regions with increases in the amount of impregnated ZnCl₂: raising the ZnCl₂/CMC mass ratio from 0.00 to 0.50 resulted in a 19-fold increase in micropore volume (V_me ^D) but caused no change in the mesopore volume (V_me ^D); increasing the ZnCl₂/CMC mass ratio from 0.50 to 1.00 led to an increment in V_mi ^D of about 50% and in V_me ^D of 170%; while raising the ratio from 1.50 to 2.50 caused a slight decrease in V_mi ^D but a 200% increment in the value of V_me ^D.     

Study on desulfurization performance of MnO<Subscript>2</Subscript>-based activated carbon from waste coconut shell for diesel emissions control

Increasing concern about the air pollution caused by sulfur dioxide (SO₂) from diesel exhaust has resulted in the improvement of low-temperature desulfurization materials for the combined SO₂ trap. In this study, coconut shell activated carbon (AC) is pretreated by nitric acid to prepare MnO₂-based activated carbon materials for SO₂ removal. The prepared materials are characterized intensively by SEM, TEM, BET, XRD, FTIR, and XPS. The SO₂ capture capacity of these materials are measured at low temperature by thermogravimetry, and the SO₂ equilibrium adsorption characteristic is also investigated. The results show that the concentrations of nitric acid do not significantly change the textural properties of MnO₂-based AC materials. The content of surface-oxygenated groups (carbonyl carbon and transition) initially increases with the HNO₃ concentration rising and reaches the maximum value when the HNO₃ concentration is 10 mol/L, resulting in the enhancement of the SO₂ capture capacity. SO₂ capture capacity of MnO₂-based activated carbon decreases after regeneration and keeps stable after several cycles of thermal regeneration. The experimental data for SO₂ adsorption on MnO₂-based AC composite can fit the Freundlich model well in comparison with Langmuir model.     

Photochemical Kinetic Modeling of Degradation of Aqueous Polyvinyl Alcohol in a UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Photoreactor

This study presents a photochemical kinetics model to describe the degradation of water-soluble PVA (Polyvinyl Alcohol) polymer in a UV/H₂O₂ batch reactor. Under the effect of UV light, the photolysis of hydrogen peroxide into hydroxyl radicals can generate a series of polymer scission reactions. For a better understanding and analysis of the UV/H₂O₂ process in the cracking of the PVA macromolecules, a chemical reaction mechanism of the degradation process and a relevant photochemical kinetics model are developed to describe the disintegration of the polymer chains. Taking into account the probabilistic fragmentation of the polymer, the statistical moment approach is used to model the molar population balance of live and dead polymer chains. The model predicts the PVA molecular weight reduction, the acidity of the solution, and hydrogen peroxide residual. In addition to previously published data collected in this laboratory, a new set of experiments were conducted using a 500 mg/L PVA aqueous for different hydrogen peroxide/PVA ratios for model validation. Measurements of average molecular weights of the polymer, hydrogen peroxide concentrations and pH of the PVA solution were determinant factors in constructing a reliable photochemical model of the UV/H₂O₂ process. Experimental data showed a decrease in the PVA molecular weight and a buildup of the solution acidity. The experimental data also served to determine the kinetics rate constants of the PVA photochemical degradation and validate the model whose predictions are in good agreement with data. The model can provide a comprehensive understanding of the impact of the design and operational variables.     

Preparation and characterization of mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> recovered from aluminum cans waste and its use in the dehydration of methanol to dimethyl ether

The present study includes synthesis of two γ-Al₂O₃ samples from waste aluminum cans using a simple precipitation method. Precipitation was carried out using two different precipitating agents (i.e. NaOH and NH₄OH). The two prepared alumina samples were characterized by means of X-ray diffraction (XRD) and N₂ adsorption–desorption techniques. Surface acidity of γ-Al₂O₃ samples was measured by adsorption of two different probe molecules (i.e. pyridine and dimethyl pyridine) followed by desorption measurements using thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Catalytic activity of the two prepared alumina samples towards the dehydration of methanol (to dimethyl ether) was studied in a fixed bed reactor at 300 °C. For comparison reasons, commercial γ-Al₂O₃ sample was, also, tested for the same catalytic reaction under the same conditions. Results showed that the alumina sample prepared using NaOH as a precipitating agent exhibited a better catalytic activity and stability compared with that prepared using NH₄OH and showed a similar activity as the commercial γ-Al₂O₃ sample.     

Green Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Cellulose/Polyvinyl Alcohol Hybride Aerogel and Its Application for Dye Removal

A novel Fe₃O₄/cellulose–polyvinyl alcohol (PVA) aerogel was successfully synthesized by an eco-friendly and facile method in this work. Cellulose/PVA matrix was prepared through an environmental friendly physical cross-linking process and further in-situ decorated with Fe₃O₄. Series of Fe₃O₄ decorated aerogels were prepared and the effects of Fe₃O₄ nanoparticles (NPs) on the aerogels were systematic investigated. As-prepared aerogels exhibited desirable properties including nanostructure, relatively high porosity, improved mechanical and superparamagnetism. The TEM results showed that Fe₃O₄ NPs were integrated in the three-dimensional matrix of cellulose/PVA with a diameter of 9–12 nm. Furthermore, the mechanical strength of the aerogels was significantly enhanced after the introduction of Fe₃O₄ NPs. Meanwhile, the obtained Fe₃O₄/cellulose/PVA aerogel exhibited excellent adsorption performance toward methyl blue dye, and can be reused through fenton-like catalysts oxidative degradation of organic dye in H₂O₂ solution. Therefore, they will have a great potential application as eco-friendly and economical adsorbents.     

Selective catalytic reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> using RDF char and municipal solid waste char based catalyst

Experiments were performed in order to investigate the possibility for the development of catalysts for low-temperature selective catalytic reduction (SCR) using municipal waste char and RDF byproduct. Physical and chemical activations, using water, and HCl and KOH, were employed to increase the catalytic activities. The characteristics of the activated catalysts were investigated using N₂ adsorption–desorption and FT-IR. The catalysts activated chemically using basic treatment showed higher NO _x removal efficiencies than those activated physically or chemically using acidic treatment. The de-NO _x performance of the activated catalysts was dependent on the chemical properties, such as oxygen functional groups as well as physical properties, such as specific surface area and pore volume. In order to investigate the effect of MnO _x , which has been reported to be efficient for the removal of NO _x in low-temperature SCR processes, the chemically activated catalyst was impregnated with manganese. The Mn-impregnated catalyst had the highest NO _x conversion at all of the temperatures tested in this study.     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

Fabrication of Biodegradable Superabsorbent Using RSM Design for Controlled Release of KNO<Subscript>3</Subscript>

Present study envisaged the sequential experimental design approach for the development of biodegradable Gelatin-Tapoica/polyacrylamide superabsorbent. Percentage water uptake efficacy of candidate sample was optimized using Response Surface Methodology (RSM) design under microwave irradiation. Different process variables such as potassium persulphate and ammonium persulphate (KPS:APS) ratio, pH, reaction time concentration of acrylamide and N,N-methylene-bis-acrylamide (MBA) were investigated as a function of percentage swelling using sequential experimental design. Maximum liquid efficacy of 1550% was obtained at KPS:APS?=?1.0:0.5; acrylamide?=?7.67?×?10^?1 mol L^?1; MBA?=?1.76?×?10^?2 mol L^?1; pH 10 and time?=?110 s. The 3D crosslinked network formed was characterized using Fourier Transformation Infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopic (SEM) techniques and thermal stability was ensured by Thermal gravimetric Analysis/Differential Thermal Analysis/Differential Thermal Gravimetric (TGA/DTA/DTG) studies. Superabsorbent synthesized could increase the moisture content in different type of soils and was found to enhance the water-holding capability of the soil upto 60 days in clayey, 40 days in sandy and 51 days in mixture of two soils under controlled conditions. Further, candidate polymer was investigated for the in-vitro controlled release of the KNO₃ with diffusion exponent ‘n’ was found to be 0.4326 indicating Fickian type diffusion. Also, initial diffusion coefficient (D_I?=?3.49?×?10^?5 m² h^?1) was found to be greater than the lateral diffusion coefficient (D_L?=?3.76?×?10^?6 m² h^?1) indicated rapid release of KNO₃ during initial hours with slow release afterwards. The ecofriendly nature of the synthesized polymer was also tested by conducting biodegradation studies and it was found to degrade upto 94% and 88.1% within 70 days with degradation rate of 1.34 and 1.26% per day using composting method and vermicomposting method respectively. So, the synthesized candidate polymer was found to be boon for agriculture-horticulture sector with wide applicability.     

High Toughness and Fast Crystallization Poly(Lactic Acid)/Polyamide 11/SiO<Subscript>2</Subscript> Composites

A poly(lactic acid) (PLA)/polyamide 11 (PA11)/SiO₂ composite was mixed from PLA, PA11, and nanosilica particles through twin-screw extrusion. The PLA/PA11/SiO₂ composite was evaluated with tensile and Izod impact tests, light transmission and haze measurement, and isothermal and nonisothermal crystallization behavior determinations. The PLA/PA11/SiO₂ (97.0/3.0) composite had approximately 10.8% less ultimate tensile strength than neat PLA, but it had greater ductility and approximately ninefold greater elongation at break. A dimple morphology was observed on the fractural surface of the PLA/PA11/SiO₂ composite, indicating that the incorporation of PA11 and nanosilica particles increased the ductility of the PLA matrix. PLA with less than 3 wt% of PA11 and 0.5 phr of nanosilica particles had an Izod impact strength of 8.72 kJ/m². PA11 and nanosilica particles effectively toughened this PLA polymer; they accelerated both isothermal and nonisothermal crystallization rates and increased the crystallinities of the resulting composites under isothermal and nonisothermal crystallization processes.     

Reductive decomposition of waste gypsum with SiO<Subscript>2</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> additives

From the point of view of a sustainable and environment-friendly society based on the recycling of material resources, it is preferable to utilize waste gypsum as a substitute for lime, which is currently produced by the calcination of limestone. In the present work, the reductive decomposition of CaSO₄ was investigated under an atmosphere of CO: 2 vol%, CO₂: 30 vol%, with N₂ as a carrier gas without and with the addition of SiO₂, Al₂O₃, or Fe₂O₃. It was found that the decomposition temperature of CaSO₄ was significantly reduced from 1673 K to 1223 K when only 5 wt% Fe₂O₃ was added to CaSO₄. In the case of the addition of SiO₂ or Al₂O₃ to CaSO₄, the decomposition temperature was reduced from 1673 K to 1623 K. This was due to the formation of composite oxides (calcium ferrite, calcium silicate, or calcium aluminate) during the reaction of CaSO₄ with the additives at a lower temperature. In addition, the formation of unfavorable product CaS was inhibited in the presence of 5 wt% Fe₂O₃, and this inhibition effect further increased as the addition of Fe₂O₃ was increased. In contrast, no significant effect on the inhibition of CaS formation was observed on the addition of SiO₂ or Al₂O₃.     

The mixing and segregation characteristics of rice straw in a cylindrical bubbling fluidized bed

In the present study, an experiment was performed to investigate the mixing and segregation characteristics of standard sand and rice straw particles in a cylindrical bubbling fluidized bed. The mass ratio (rice straw/standard sand = 0.5–1.25 %) of two particles and superficial gas velocity (0.13–0.18 m/s) were changed as experimental variables. The pressure drop curve and Kramer’s equation were used to determine the minimum fluidization velocity and mixing index, respectively. In all cases, the mixing index was the lowest at U/U _mf = 1.15. Based on the point of U/U _mf = 1.15, the segregation region and mixing region were observed. In the segregation region, mass ratio of 0.75 % showed the lowest mixing index. At the U/U _mf = 1.23 which was selected as the starting of fast pyrolysis considering residence time and the previous fast pyrolysis experiment, mass ratio of 1.25 % showed the highest mixing index which was 0.90.     

Effect of Nano-SiO<Subscript>2</Subscript> and Bark Flour Content on the Physical and Mechanical Properties of Wood–Plastic Composites

The aim of this study is to evaluate the impact of nano-SiO₂ and bark flour (BF) on the natural fiber–plastic composites engineering properties made from high density polyethylene (HDPE) and beech wood flour (WF). For this purpose, WF and BF in 60 mesh size and weight ratio of (50, 0 %), (30, 20 %), (10, 40 %) and (0, 50 %) respectively were mixed with HDPE. In order to increase the interfacial adhesion between the filler and the matrix, the maleic anhydride grafted polyethylene was constantly used at 3 wt% for all formulations as a coupling agent. The nano-SiO₂ particles with weight ratio of 0, 1, 2, and 4 % were also utilized to enhance the composites properties. The materials were mixed in an internal mixer (HAAKE) and then the bark and/or wood–plastic composite samples were made utilizing an injection molding machine. The physical tests including water absorption and thickness swelling, and mechanical tests including bending characteristics and un-notched impact strength were carried out on the samples based on ASTM standard. The results indicated that as the BF content increased in the composite, mechanical and physical properties were reduced, but the given properties were increased with the addition of nano-SiO₂. The addition of nano-SiO₂ had a negative impact on the physical properties, but when it was up to 2 %, it increased the impact strength.     

Investigation of Biosurfactant Activity and Asphaltene Biodegradation by <Emphasis Type="Italic">Bacillus cereus</Emphasis>

In this research, a biosurfactant-producing bacterium with capability of asphaltene degradation was isolated from oil-contaminated soil samples, and identified as Bacillus cereus. This strain produced an effective biosurfactant in the presence of molasses and the surface tension was reduced to the level of 36.4 mN/m after 48 h under optimum conditions. The optimum values of carbon-to-nitrogen ratio (C:N), pH, and temperature for biosurfactant production were determined as 30:1, 7.3 and 29 °C, respectively, using response surface methodology. The maximum emulsification activity in the culture broth was 53 % after 48 h using kerosene at 25 °C. The goodness of fit of four growth kinetic models including Tessier, Contois, Logistic and Westerhoff was compared for the bacterial growth and molasses utilization of B. cereus in 5-L batch bioreactor during 120 h. Conducted kinetic study showed that biosurfactant production had a good fit with the Contois growth kinetic model (R² = 0.962) and the maximum specific growth rate (µ _max ), saturation constant (K _s ) and the yield of biomass per substrate (Y _x/s ) were determined to be 0.145 h^?1, 1.83 g/L and 0.428 g/g, respectively. The asphaltene biodegradation in flask was evaluated by FTIR analysis and quantified by a spectrophotometer. This bacterium was able to degrade up to 40 % of asphaltene as a sole carbon and energy source after 60 days at 28 °C. The resulting surface tension of 30.2 mN/m with the critical micelle concentration of 23.4 mg/L indicated good efficiency of the biosurfactant.     

PM<Subscript>10</Subscript> and Ultrafine Particles Counts In-Vehicle and On-Road in the Athens Area

This work presents the first results of a study concerning on-road and in-vehicle exposure to particulate matter in the area of Athens. PM₁₀ concentration measurements were conducted by TSI DustTrak, while driving along routes with different characteristics of traffic density, during September 2003–March 2004. Concurrent measurements of the ultrafine particles (UFPs) number concentration were also conducted, by condensation particle counter during part of the days. Pedestrian exposure to PM₁₀ and UFPs was also studied through stationary measurements on the kerbside of selected roads on November 2003 and February 2004. A major avenue, a heavy-trafficked road across a children hospital and two central roads, one in a residential and one in a commercial area were selected for measurement. The results indicate that every day commuters are exposed to significant concentration levels. Higher exposures were observed in heavy-trafficked areas and during rush hours. Mean PM₁₀ in-vehicle and on-road concentrations ranged from 30–320 μg/m³ and 70–285 μg/m³, respectively. The ultrafine particles number concentrations were in the range of 5.0 × 10⁴–17.3 × 10⁴ particles/cm³ in-vehicle and 3.1 × 10⁴–7.3 × 10⁴ particles/cm³ on the kerbside of a central residential road. Both PM₁₀ and UFPs concentrations presented repeated short-term peak exposures. The results clearly point out the importance of the road microenvironment (in-vehicle and on kerbside) for population exposure in urban areas.     

Photocatalytic Degradation of Poly(Vinyl Alcohol) on Pt/TiO<Subscript>2</Subscript> with Fenton Reagent

In this research Fenton reagent (Fe²⁺/H₂O₂) was investigated as oxidants to degrade poly (vinyl alcohol) (PVA). The role of nano-TiO₂ photocatalyst was discussed as an additive in Fenton reagent (Fe²⁺/H₂O₂). Pt/TiO₂ composites were also synthesized by photo-reaction to be used as additive in Fenton reagent. The rapid degradation of PVA was obtained when Pt/TiO₂ composites served as photocatalyst. The different photocatalytic efficiency of Pt/TiO₂- Fenton reagent (Fe²⁺/H₂O₂) was studied compared with TiO₂- Fenton reagent (Fe²⁺/H₂O₂) during the degradation of PVA.     

Coal fly ash based carbons for SO2 removal from flue gases

Two different coal fly ashes coming from the burning of two coals of different rank have been used as a precursor for the preparation of steam activated carbons. The performance of these activated carbons in the SO₂ removal was evaluated at flue gas conditions (100 °C, 1000 ppmv SO₂, 5% O₂, 6% H₂O). Different techniques were used to determine the physical and chemical characteristics of the samples in order to explain the differences found in their behaviour. A superior SO₂ removal capacity was shown by the activated carbon obtained using the fly ash coming from a subbituminous–lignite blend. Experimental results indicated that the presence of higher amount of certain metallic oxides (Ca, Fe) in the carbon-rich fraction of this fly ash probably has promoted a deeper gasification in the activation with steam. A more suitable surface chemistry and textural properties have been obtained in this case which explains the higher efficiency shown by this sample in the SO₂ removal.     

Synthesis,Characterization and NH<Subscript>3</Subscript>/N<Subscript>2</Subscript> Gas Permeation Study of Nanocomposite Membranes

Carbon nanotubes have exceptional mechanical properties which make them very attractive for the development of composite membranes. In this research, NH₃/N₂ gas permeation behavior of flat sheet composite membranes was examined. The cellulose acetate-multiwalled carbon nanotubes composite membranes were synthesized using solution casting method. The morphology and dispersion of carbon nanotubes were observed through SEM. However, the composite membranes were also characterized using several analytical techniques such as X-ray diffraction analysis, tensile testing analysis, and thermal gravimetric analysis. Characterization of these membranes depicted that carboxylic group functionalized MWCNTs are extremely compatible with CA. The permeation experiments were performed with NH₃ and N₂ to explore the host–guest interaction of MWCNTs with chosen gases. The permeability of NH₃ was found pronounced compared to N₂. The NH₃/N₂ selectivity up to 90 was documented.     

Agricultural waste biomass converted to activated carbon as a material for gold processing

Waste biomass in the form of coconut shells was pyrolyzed and activated with steam to produce activated carbons, which were then assessed for their potential for use in the processing of gold. Activated carbons with different amounts of carbon burn-off were prepared by steam activation of carbonized coconut shells. Carbonization of the shells was performed at a pyrolysis temperature of 600?°C and the resulting chars were activated in steam at a gasification temperature of 900?°C and various durations of activation time. Textural characteristics of the derived activated carbons were determined and their effects on gold adsorption from an acidified gold chloride solution were studied. The surface area and porosity of the activated carbons increased with activation time up to 59 wt?% carbon burn-off. A further increase in the burn-off resulted in the loss of structural walls between pores and consequently, a decline in the surface area and porosity of the activated carbons. The gold adsorption capacity and rate of gold adsorption from the gold chloride solution onto the activated carbons were found to increase significantly with the total pore and micropore volumes of the activated carbons.     

Influence of H<Subscript>2</Subscript> on the decomposition of halides by nonthermal plasma incorporated with in situ alkaline absorption

To control the emission of halides into the environment, an experiment on the nonthermal plasma decomposition of the halides CF₄, CHF₃, C₂HCl₃, and CHClF₂ was conducted in a wire-in-tube corona reactor. It was found that the decomposition of C₂HCl₃ and CHClF₂ was easy compared with the decomposition of CF₄ and CHF₃. With the addition of H₂ in N₂ gas, the decomposition ratio of CF₄, C₂HCl₃, and CHClF₂ increased. In contrast, the decomposition ratio of CHF₃ in a hydrogen-rich atmosphere was lower than that in an N₂ atmosphere. It was demonstrated that the yields of HF and/or HCl formed during halide decomposition clearly increased in the presence of H₂ in N₂ gas. Furthermore, in order to prevent the production of unwanted products from halide decomposition, a combination of plasma decomposition and in situ alkaline absorption was devised by coating a layer of Ca(OH)₂ onto the surface of the grounding electrode. It was demonstrated that the Ca(OH)₂ sorbent played an effective role as a scavenger, participating in halide decomposition by capturing reaction products such as HCl and HF, therefore resulting in increased halide decomposition.