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.     

Identification and Model Predictive Control (MPC) of Aqueous Polyvinyl Alcohol Degradation in UV/H2O2 Photochemical Reactors

Journal of Polymers and the Environment - The performance of two continuous UV/H2O2 photoreactors in series under unsteady-state condition is studied. An input–output dynamic model is...     

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.     

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.     

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.     

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.     

Preparation and characterization of high surface area activated carbon from pine wood sawdust by fast activation with H<Subscript>3</Subscript>PO<Subscript>4</Subscript> in a spouted bed

Activated carbons were produced from waste pine wood sawdust using fast activation with H₃PO₄ in a spouted bed. In this study, activation temperature was set as 800 °C, and activation time ranged from 1 to 15 min. Experimental results show that sawdust impregnated with higher mass ratio of H₃PO₄ would be agglomerated in spouted bed, and difficult to fluidize. Therefore, an amount of quartz sand was added to assist for good fluidization. Fluidization of particle can improve the BET surface area or micropore volume of activated carbons. High BET surface area activated carbons can be obtained with activation time of only 1–5 min by combining the fluidization and H₃PO₄ fast activation. The obtained activated carbons contained developed pore structure and abundant surface functional groups (carboxyl, carbonyl and P-containing groups) by SEM–EDS, FTIR and XPS techniques. The particles of impregnation ratio of 1:1 can achieve fluidization without adding the quartz sand, which was convenient for experimental operation and even industrial production, and the BET surface area can reach more than 1000 m²/g in activation time of only 5 min.     

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.     

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.     

Effect of Nanoscale SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> as the Fillers on the Mechanical Properties and Aging Behavior of Linear Low-Density Polyethylene/Low-Density Polyethylene Blends

Linear low-density polyethylene (LLDPE) was blended with low-density polyethylene (LDPE) at a fixed ratio (80 wt LLDPE and 20 wt %LDPE) and filled with nanoparticles of SiO₂ and TiO₂ at a ratio up to wt 5%, so as to develop the polymeric composites suitable to preparing the agricultural micro-irrigation pipes having good environmental adaptability. These compounds were blended using calcium stearate, polyethylene wax, and titanate coupling agent as the auxiliary dispersants, and ethylene-vinyl acetate copolymer (EVA) as the toughness improver. The LLDPE/LDPE composites filled with the nanoparticles were extruded and injected to prepare the composites specimens for the performance evaluations and micro-irrigation pipe field test. The mechanical properties, thermostability, and processibility of the injected composites were investigated. The effect of heating in an oven and irradiating by ultraviolet on the mechanical properties of the composites was explored. The environmental adaptability of the micro-irrigation pipes made of the filled LLDPE/LDPE composites was evaluated making use of long-term outdoor field test in northwest China where the arid and harsh natural conditions are of great concerns. It was found that the LLDPE/LDPE blend with the LLDPE mass fraction fixed as 80% showed balanced mechanical and thermal properties and flexibility, and was suitable to be used as the basic resin matrix. The incorporation of nano-TiO₂ contributed to effectively improving the resistance to heating and ultraviolet irradiation of the composites. The composite made from 91% basic resin matrix, 6% EVA, and 3% mixed nano-SiO₂ and TiO₂, showed balanced comprehensive properties. The micro-irrigation pipes made of this filled LLDPE/LDPE composite had good environmental adaptability and service behavior in a three-year field test and were suitable to be used in arid area.     

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.     

Whole-year-round Observation of N<Subscript>2</Subscript>O Profiles in Soil: A Lysimeter Study

Despite many studies of the N₂O emission, there is a lack of knowledge on the role of subsoil for N₂O emission, particularly in sandy soils. To obtain insight into the entrapment, diffusion, convection and ebullition of N₂O in the soil, the N₂O concentration in the soil atmosphere was measured over a period of 1 year in 4 lysimeters (agricultural soil monoliths of 1 m2 × 2 m) at 30, 50, 80, 155, and 190 cm depth with altogether 86 gas probes. Additionally the N₂O emission into the atmosphere was measured in 20 closed chambers at the soil surface. Concurrently the soil temperature and soil water content were recorded in order to quantify their effects on the fate of N₂O in the soil. Results of the continuous measurements between January and December 2006 were: N₂O concentrations were highest in the deeper soil; maximum concentration was found at a depth of 80 cm, where the water content was high and the gas transport reduced. The highest N₂O concentration was recorded after ‘special events’ like snowmelt, heavy rain, fertilization, and grubbing. The combination of fertilization and heavy rain led to an increase of up to 2,700 ppb in the subsoil.     

Tensile and Combustion Properties of PP/IFR/POE/nano-CaCO<Subscript>3</Subscript> Composites

The tensile and combustion properties of polypropylene/polyolyaltha olefin composites filled with intumescent flame retardant (IFR) and nanometer calcium carbonate (nano-CaCO₃) were measured. It was found that the values of the Young’s modulus of the composites increased almost linearly, while the values of the tensile yield strength and tensile fracture strength of the composites decreased with increasing the IFR weight fraction; the values of the elongation at break of the composites decreased quickly when the IFR weight fraction was lower than 10 wt%, and then varied slightly when the IFR weight fraction was higher than 10 wt%. Moreover, the morphology of the specimens after combustion was observed and the frame retardant mechanisms of the composites were discussed.     

Biodegradable Composite Foams of PLA and PHBV Using Subcritical CO<Subscript>2</Subscript>

One key strategy for increasing the application potential for biodegradable plastics lies in improving the physical and mechanical characteristics, which can be attained by inducing a cellular morphology in the pure polymer with the aid of a blowing agent, as well as by blending two or more polymers with the desirable properties. This paper examines the effect that blending two biodegradable polymers has on the thermal properties and morphology of the resultant foams blown with carbon dioxide (CO₂). Polylactic acid (PLA), polyhydroxybutyrate-co-valerate (PHBV) and blends of both were foamed and characterized in terms of thermal characteristics, relative density, cell size, and foam morphology. The results indicate that although PLA and PHBV are immiscible, the presence of small quantities of PHBV (25 wt%) could lead to low density foams with finer, more uniform cells. Furthermore, the crystallinity of PHBV was found to be unaffected by the presence of PLA in the composite, which supports the immiscibility of PLA and PHBV.     

Preparation of Water-Insoluble Antibacterial Materials with Surface-Grafted Material PSt/SiO<Subscript>2</Subscript> and Their Antibacterial Activity

Styrene (St) was graft-polymerized onto the surfaces of micro-sized silica gel particles, and the surface-grafted composite particles PSt/SiO₂ were obtained. With the surface-grafted composite particles PSt/SiO₂ as a starting material, water-insoluble antibacterial materials with quaternary ‘onium’ salt-type were synthesized via two polymer reaction steps. The grafted polystyrene was first chloromethylated, resulting in grafted particles CMPS/SiO₂, and then quaterisation (QN) and quaternary phosphonium reaction (QP) were conducted with triethylamine, tri-n-butylamine and triphenyl phosphine as reagents, respectively. Two kinds of water-insoluble antibacterial materials, QN-PSt/SiO₂ and QP-PSt/SiO₂ were prepared. Their antibacterial property was mainly investigated by using Escherichia coli (E. coli) as a model bacterium and by adopting colony count method. The relationship between the chemical structure of the antibacterial group and antimicrobial activity for the water-insoluble antibacterial materials was studied in detail, and their antibacterial mechanism was investigated by TTC-dehydrogenase activity determination and extracellular DNA and RNA measurement methods. The experimental results show that QN-PSt/SiO₂ and QP-PSt/SiO₂ possess strong antibacterial activity. The main factors affecting the antibacterial ability of the water-insoluble materials are the chemical structure of the antibacterial groups, the bound density of the antibacterial groups on the surface of the water-insoluble antibacterial materials as well as the pH value of the medium. QP-PSt/SiO₂ has stronger antibacterial activity than QN-PSt/SiO₂; the QN-PSt/SiO₂ prepared with tri-n-butylamine has stronger antibacterial activity than that prepared with triethylamine; the water-insoluble material with higher bound density of the antibacterial groups has stronger antibacterial ability; as the pH value of the medium is over the isoelectric point of E. coli, the antibacterial ability is strengthened with the increase of pH value.     

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.     

Conversion of Mixed Low-Density Polyethylene Wastes into Liquid Fuel by Novel CaO/SiO<Subscript>2</Subscript> Catalyst

Plastic wastes disposal can be done by various methods such as landfill, incineration, mechanical and chemical recycling but these are restricted due to some environmental, economic and political problems. Conversion of these plastic wastes into valuable products by degradation is the best option. In the present work waste low density polyethylene was degraded by catalytic process using CaO/SiO₂ as mixed catalyst. The conditions for catalytic degradation were optimized for the production of maximum liquid fuel. It was found that the yield of liquid product was up to 69.10 wt% at optimum condition of temperature (350 °C), time (90 min) and catalyst feed ratio (1:0.4). Liquid fuels obtained from the catalytic degradation were further separated into various fractions by fractional distillation. Composition of liquid fuels was analyzed by FTIR spectroscopy, which showed that the liquid fuels mostly consist of paraffinic and naphthenic hydrocarbons. Different fuel properties such as density, specific gravity, American petroleum institute gravity (API gravity), viscosity, kinematic viscosity, refractive index, refractive intercept and flash point of both the parents and various fractional fuels were determined. All the properties of the obtained fuels are in close agreement with the fuel properties of gasoline, kerosene and diesel. It was found that our catalyst is very much efficient in terms of time, degradation temperature and amount of catalyst.     

Production of natural and recycled aggregates: the environmental impacts of energy consumption and CO<Subscript>2</Subscript> emissions

Natural aggregates (NA) are crushed and processed in crushing plants after the extraction stage in quarries. In the present study, the aggregates are divided into three scenarios, depending on the production methods. The first scenario considers the production of NA, the second scenario deals with the production of recycled aggregates (RA) with respect to construction and demolition waste, and the third scenario, which is a hybrid scenario, handles the combination of NA and RA by assuming a 50% mixing percentage. In this research, we assess the environmental impacts on the production of aggregates via each scenario, using life cycle assessment; in addition, energy consumption and CO₂ emissions are considered as the environmental variables. We conclude that Iran’s current policy with an annual energy consumption of 1.48 million tons of oil equivalent (toe) can have a footprint of 2.88 million tons of CO₂ eq emissions per year (the first scenario). Achieving 30 and 36% reduction in annual energy consumption and CO₂ emissions, respectively, by the third scenario compared to the first scenario indicates the destructive effect of the first scenario from the environmental outlook.     

Absorption behavior of chlorine and sulfur by Ca(OH)<Subscript>2</Subscript> under simulated conditions with a fluidized bed combustor

This study was carried out to investigate the absorption reaction of chlorine and sulfur with Ca(OH)₂ under simulated conditions related to the co-combustion of refuse-derived fuel and sewage sludge in the fluidized bed combustor, such as high temperature, moisture and a mixing of samples. The combustion experiments were carried out in an electrical furnace with PVC and sulfur powders as the waste samples. High-purity slaked lime powder was used to capture the chlorine and sulfur. The experimental results showed that the removal efficiencies of both chlorine and sulfur were over 90% when the mole ratios of Ca on Cl and S were over 2.5. Furthermore, simultaneous absorption was helpful in improving the removal efficiency of chlorine and sulfur. The presence of chlorine markedly increased the removal efficiency of sulfur. The removal efficiency of chlorine was the highest at 700°C in both independent and simultaneous absorption. The removal efficiency of sulfur increased as the temperature increased, but the removal efficiency of chlorine sharply decreased from 95 to 83% when the moisture content in gases increased from 0 to 20 vol%. These results were confirmed by the combustion test of granular CaCl₂.     

Physical Characterization of Biodegradable Films Based on Chitosan,Polyvinyl Alcohol and <Emphasis Type="Italic">Opuntia</Emphasis> Mucilage

This study aimed to develop and characterize biodegradable films containing mucilage, chitosan and polyvinyl alcohol (PVA) in different concentrations. The films were prepared by casting on glass plates using glycerol as plasticizer. Mechanical properties, water vapor and oxygen barrier, as well as the interaction with water, were measured. The compatibility of the film-forming components and the uniformity of the films were determined by zeta potential and SEM, respectively. The glycerol and mucilage allowed obtaining more hydrophilic films. The barrier properties of the films made from 100 % chitosan were similar to composed films containing PVA up to 40 %. The results of this study suggest that the interaction between chitosan and mucilage could increase water vapor permeability. The films prepared from either 100 % chitosan or PVA showed a more hydrophobic behavior as compared to the composed films. The films were homogenous since no boundary or separation of components was observed, indicating a good compatibility of the components in the films.