Chemical Recycling of Polyamide Waste at Various Temperatures and Pressures Using High Pressure Autoclave Technique

Chemical recycling of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 150, 200, 210, 220,230 and 240 °C and at various pressures of 100, 200, 300, 400, 500, 600 and 700 psi (pound per square inch). Viscosity average molecular weight of the polyamide waste sample was determined by Ostwald method and recorded as 1.928 × 10³. The reaction was found to be first order with velocity constant in order of 10⁻² min⁻¹. The velocity constant and percent conversion of depolymerization reaction at 240 °C and 700 psi pressure were recorded as 2.936 × 10⁻² min⁻¹ and 99.99% respectively. The velocity constant was obtained on the basis of measurement of amine value. Kinetic and thermodynamic parameters such as energy of activation, frequency factor, enthalpy of activation were found to be 10.6 kJ mole⁻¹, 0.3719 min⁻¹ and 6.3 kJ mole⁻¹ respectively, at the optimum conditions for maximum depolymerization of polyamide waste.     

Kinetics and Thermodynamics of Hydrolytic Depolymerization of Polyamide Waste at Various Temperature and Autogenious Pressure by High-Pressure Autoclave

Hydrolytic depolymerization of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 235, 240, 245, 250 °C and at autogenious pressure 480, 500, 520, and 600 psi (pound per square inch).The reaction rate constant, energy of activation, enthalpy of activation, entropy of activation and equilibrium constant were calculated from the experimental data obtained. The maximum depolymerization (59.2%) of polyamide waste into monomer caprolactum was obtained at 250 °C and 600 psi pressure. The reaction rate constant was obtained on basis of measurement of amine value and residual weight. The depolymerization reaction was found to be pseudo first order with reaction rate constant of the order of 10⁻³ min⁻¹. The enthalpy, entropy and free energy of activation were recorded as 85.75, −0.1354 and 156.59 kJ mol⁻¹ respectively at the experimental conditions for maximum depolymerization of polyamide waste. The thermodynamic equilibrium constant for this hydrolysis reaction was found to be 2.3 × 10⁻¹⁶.     

The Effect of Extraction Conditions on the Chemical Characteristics of Pectin from Opuntia ficus indica Cladode Flour

Pectin from the cladode flour of Opuntia ficus indica was extracted at different ethylenediaminetetraacetate concentrations (10 or 20 %), temperatures (40 or 80 °C), pH values (2 or 11), and times (10, 20, 30 40, 50 or 60 min). The effects of the extraction conditions on the yield, purity, and chemical composition of pectin were assessed. The highest pectin yield was observed for pectin obtained under alkaline conditions and 20 % of EDTA. However, pectin produced from alkaline extractions had a lower content of GalA than pectin produced from acid extractions. Higher temperatures favored the extraction of pectin under acid conditions, but these conditions diminished the arabinose content of pectins in a time-dependent manner. The tested extraction conditions caused only slight changes in the molecular weight of the extracted pectin as a function of time.     

Performance and suitability of a landfill bioreactor with low cost biofilm contained clay-waste polyethylene-clay composite liner system for tropical climates of Asian countries

The objective of the study was to develop a low cost and environmentally friendly liner system for a landfill bioreactor to harness energy from waste. The landfill bioreactor test cell was constructed and evaluated for performance under dry tropical conditions of Sri Lanka. The research was carried out from March 2009 to September 2010. The clay-waste polyethylene-clay composite liner system was developed and permeability was tested. The permeability values of the liner under both saturated and unsaturated conditions at the high estimated hydraulic head of 86.2 cm were in between 6.3 × 10⁻⁸ and 2.6 × 10⁻⁸ cm/s. The permeability of the liner under waste filled condition varied between 2.17 × 10⁻⁹ and 8.15 × 10⁻⁹ cm/s, which satisfies the standard permeability value. Thus, the results were below the minimum requirement at very high estimated leachate head. After loading the test cell, leachate and permeate characteristics were analyzed for 273 days, from January 2010 to September 2010. The study showed the relationships among various parameters including pH, electrical permeability, chemical oxygen demand, biological oxygen demand, ammonia, nitrate, phosphate, total solids, volatile solids, total suspended solids and volatile suspended solids. The results of the analysis indicated that there are significant differences in the values of leachate and permeate parameters. The permeate parameters had values very much lower than those of leachate. It reveals that the clay-waste polyethylene-clay composite liner system reduced the concentration of these parameters when the leachate passed through the liner. The biofilm formed in waste polyethylene within the liner may have degraded most of organic materials found in the leachate when it passed through the liner. Therefore, the clay-waste polyethylene-clay composite liner system can be applied for full scale landfill bioreactors, particularly for Asian developing countries, due to better performance and more environmentally friendly characteristics.     

Rheological Studies of Microfibrillar Cellulose Water Dispersions

The rheological behaviour of microfibrillar cellulose (MFC) water dispersions has been investigated. For the first time a detailed study of shear dependent viscosity at low and high shear rate is presented. A peculiar time dependent behaviour measured in the area between 0 and 1000 s⁻¹ was identified. The study shows a hysteresis loop in the shear rate–viscosity relationship at low shear rate. Additional time dependent shear rate measurements were performed, and a hypothesis for a mechanism of interaction and formation of a fibrils network was suggested. Higher temperature caused lower viscosity values, and this difference was increased at higher shear rate values. Oscillatory measurements showed how the closeness of the fibrils helps network creations. Data obtained from high shear measurements showed that 1% MFC water dispersions had a dilatant behaviour at ultra high shear rates with values increasing from 120 to 300 Pa s in the area between 180,000 and 330,000 s⁻¹ .     

Evaluation of a classification method for biodegradable solid wastes using anaerobic degradation parameters

We studied the biochemical and anaerobic degradation characteristics of 29 types of materials to evaluate the effects of a physical composition classification method for degradable solid waste on the computation of anaerobic degradation parameters, including the methane yield potential (L₀), anaerobic decay rate (k), and carbon sequestration factor (CSF). Biochemical methane potential tests were conducted to determine the anaerobic degradation parameters of each material. The results indicated that the anaerobic degradation parameters of nut waste were quite different from those of other food waste and nut waste was classified separately. Paper was subdivided into two categories according to its lignin content: degradable paper with lignin content of <0.05 g g VS^?1, and refractory paper with lignin content >0.15 g g VS^?1. The L₀, k, and CSF parameters of leaves, a type of garden waste, were similar to those of grass. This classification method for degradable solid waste may provide a theoretical basis that facilitates the more accurate calculation of anaerobic degradation parameters.     

Transdermal Delivery of Nicotine Using Pectin Isolated from Durian Fruit-Hulls-Based Polymer Blends as a Matrix Layer

Many natural polymers with various chemical structures are used to prepare transdermal patches. Pectin is a one interesting type of polymer because it can control drug release when used in transdermal patches. In Thailand, the waste from durian fruit-hulls is a major problem for the environment. However, the pectin from it can be isolated under acid conditions and used to prepare transdermal patches for nicotine delivery which has not yet been reported. As the isolated pectin is a natural polymer, the film made from isolated pectin is a brittle; therefore, adding a low protein natural rubber latex (LPNRL) polymer was needed to increase its flexibility. The transdermal patches were amorphous and had T_g values ranging from 81.0 to 93.3 °C. Moisture uptake, swelling ratio, and erosion values of the patches were significantly decreased after addition of LPNRL, which resulted in low hydrophilicity. The in vitro release and permeation of nicotine depends on the hydrophilicity of the patches. The kinetic models for in vitro release and permeation of nicotine were Higuchi model and zero order, respectively. In conclusion, pectin isolated from fruit-hulls of Mon Thong durians is an effective polymer to control the release of nicotine. It also is an option that could solve the environmental problems caused by durian fruit-hulls waste.     

Anaerobic co-digestion of food waste and landfill leachate in single-phase batch reactors

In order to investigate the effect of raw leachate on anaerobic digestion of food waste, co-digestions of food waste with raw leachate were carried out. A series of single-phase batch mesophilic (35 ± 1 °C) anaerobic digestions were performed at a food waste concentration of 41.8 g VS/L. The results showed that inhibition of biogas production by volatile fatty acids (VFA) occurred without raw leachate addition. A certain amount of raw leachate in the reactors effectively relieved acidic inhibition caused by VFA accumulation, and the system maintained stable with methane yield of 369–466 mL/g VS. Total ammonia nitrogen introduced into the digestion systems with initial 2000–3000 mgNH₄–N/L not only replenished nitrogen for bacterial growth, but also formed a buffer system with VFA to maintain a delicate biochemical balance between the acidogenic and methanogenic microorganisms. UV spectroscopy and fluorescence excitation–emission matrix spectroscopy data showed that food waste was completely degraded.We concluded that using raw leachate for supplement water addition and pH modifier on anaerobic digestion of food waste was effective. An appropriate fraction of leachate could stimulate methanogenic activity and enhance biogas production.     

Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10⁻⁴mol/L) and H₂O₂ (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10⁻⁹−6.083 × 10⁻⁹ mol^1.7 L s⁻¹. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H₂O₂ was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.     

Utilization of molasses spentwash for production of bioplastics by waste activated sludge

Present study describes the treatment of molasses spentwash and its use as a potential low cost substrate for production of biopolymer polyhydroxybutyrate (PHB) by waste activated sludge. Fluorescence microscopy revealed the presence of PHB granules in sludge biomass which was further confirmed by fourier transform-infra-red spectroscopy (FT-IR) and ¹³C nuclear magnetic resonance (NMR). The processing of molasses spentwash was carried out for attaining different ratios of carbon and nitrogen (C:N). Highest chemical oxygen demand (COD) removal and PHB accumulation of 60% and 31% respectively was achieved with raw molasses spentwash containing inorganic nitrogen (C:N ratio = 28) followed by COD removal of 52% and PHB accumulation of 28% for filtered molasses containing inorganic nitrogen (C:N ratio = 29). PHB production yield (Y_p/s) was highest (0.184 g g^?1 COD consumed) for deproteinized spentwash supplemented with nitrogen. In contrast, the substrate consumption and product formation were higher in case of raw spentwash. Though COD removal was lowest from deproteinized spentwash, evaluation of kinetic parameters suggested higher rates of conversion of available carbon to biomass and PHB. Thus the process provided dual benefit of conversion of two wastes viz. waste activated sludge and molasses spentwash into value-added product-PHB.     

Anaerobic co-digestion of kitchen waste and fruit/vegetable waste: Lab-scale and pilot-scale studies

The anaerobic digestion performances of kitchen waste (KW) and fruit/vegetable waste (FVW) were investigated for establishing engineering digestion system. The study was conducted from lab-scale to pilot-scale, including batch, single-phase and two-phase experiments. The lab-scale experimental results showed that the ratio of FVW to KW at 5:8 presented higher methane productivity (0.725 L CH₄/g VS), and thereby was recommended. Two-phase digestion appeared to have higher treatment capacity and better buffer ability for high organic loading rate (OLR) (up to 5.0 g (VS) L^?1 d^?1), compared with the low OLR of 3.5 g (VS) L^?1 d^?1 for single-phase system. For two-phase digestion, the pilot-scale system showed similar performances to those of lab-scale one, except slightly lower maximum OLR of 4.5 g (VS) L^?1 d^?1 was allowed. The pilot-scale system proved to be profitable with a net profit of 10.173 $/ton as higher OLR (?3.0 g (VS) L^?1 d^?1) was used.     

Effect of γ-Dose rate on Biodegradation of γ-Sterilized Biomedical Polyolefins

The aim of the present study is to study the effect of γ-dose rate on the biodegradation of γ-sterilized polyolefins. Films of isotactic polypropylene, high density polyethylene and ethylene-propylene (EP) copolymer were sterilized under γ-radiation with doses of 10 and 25 kGy. Two different ⁶⁰Co sources were used with dose rate 600 and 780 Gy h⁻¹. Neat and sterilized samples were incubated in compost and fungal culture environments. The changes in functional groups, surface morphology and intrinsic viscosity in polymer chains were characterized by FT-IR spectroscopy, SEM and viscometric measurements, respectively. It was observed that both γ-degradation and biodegradation processes depend on the dose rate of γ-source. It was found that the biodegradation of γ-sterilized polyolefins in composting and microbial culture environments increased with decreasing the γ-dose rate.     

Utilization of Natural Oils for Decomposition of Polyurethanes

The model polyurethane foam and model compact polyurethane material were prepared and then decomposed by means of natural oils. Castor oil and fish oil based polyol were used in this study. Optimal conditions for the polyurethane decomposition were found. Temperature 250 °C was necessary for efficient polyurethane decomposition by castor oil whereas 200 °C is sufficient in the case of fish oil based polyol. Prepared products have hydroxyl number in the range of 95–168 mg KOH g⁻¹. During the polyurethane decomposition no cleavage of double bonds in the fatty acid chains of castor oil and fish oil based polyol was observed.     

Emission inventory of deca-brominated diphenyl ether (DBDE) in Japan

Atmospheric emissions of deca-brominated diphenyl ether (DBDE) in Japan were estimated based on the material flow of DBDE products and their emission factors. In 2002, the demand for DBDE in Japan was 2200 ton/year and the stock level was about 60 000 ton. The DBDE flow into the waste stream was estimated to be about 6000 ton/year and the flow out through second-hand product exports was more than 700 ton/year. Home appliance recycling facilities dismantle and crush domestic wastes containing about 600 ton of DBDE annually. Material recycling of crushed plastics is not commonly practiced as yet. Emission factors from plastics processing (2 × 10⁻⁹–1 × 10⁻⁷), textile processing (9 × 10⁻⁷), home appliance recycling (8 × 10⁻⁹–5 × 10⁻⁶), and waste incineration (1 × 10⁻⁷–2 × 10⁻⁶) were estimated using field measurement data. The DBDE emission rate through house dust during the service life of final products (2 × 10⁻⁷–9 × 10⁻⁷ per year) was estimated using the DBDE concentration in dust and the amount of dust in used televisions. Emission factors from previous studies were also used. The estimated total DBDE emission was 170–1800 kg/year. These results suggest the necessity of characterizing emissions during the service life of products, which is essential information for formulating an appropriate e-waste recycling strategy.     

Thiourea leaching of gold from processed municipal solid waste incineration residues

Incineration is one of the key technologies in disposal of municipal waste, which produces municipal solid waste incineration (MSWI) residues with high valuable metal contents. The recycling strategy for the MSWI residues is typically focused on the recovery of scrap metals yielding processed municipal solid waste incineration residues (PIR) as the main byproduct. However, the PIR still contains valuable metals, particularly gold, which cannot be extracted by conventional methods. Here, we evaluated the feasibility of using the 0.5–2.0 mm grain size fraction of PIR containing 28.82 ± 1.62 mg/kg of gold as raw material for a two-stage extraction process. In the first stage the alkalic fine-grained PIR was acidified with a solution of 20% (v/v) of HCl-containing flue gas cleaning liquid that is obtained by the municipal waste incineration plant itself as a waste product. In the second stage we leached the acidified fine-grained PIR by thiourea with Fe³⁺ as an oxidant. Application of the thiourea-Fe³⁺ leaching system resulted in recovery of 16.4 ± 1.56 mg/kg of gold from the fine-grained PIR within 6 h of incubation. Due to high gold market prices, upscaling of the suggested technology can represent a suitable strategy for gold recovery from PIR and other MSWI residues.

     

Biodegradation of Poly(3-Hydroxybutyrate) Produced from Cupriavidus necator with Different Concentrations of Oleic Acid as Nutritional Supplement

The environmental impact caused by the disposal of plastics has motivated the development of biodegradable materials. Recent studies showed that supplementation with oleic acid (OA) in cultures producing poly(3-hydroxybutyrate), P(3HB), increased the polymer productivity. However only few studies have shown the properties and biodegradation profile of the polymer obtained. This research investigated the influence of OA concentration on the biodegradation of the P(3HB) obtained from cultures of Cupriavidus necator. The crystallinity of the casting films determined by differential scanning calorimetry (DSC) was reduced from 70% (0 g L⁻¹ of OA) to 52% (3.0 g L⁻¹ of OA). A reduction of 11 °C in the melting temperature was observed with 3.0 g L⁻¹ of OA. The kinetic of biodegradation was: 3.0 > 1.5 > 0.9 > 0.3 > 0 g L⁻¹ of OA.     

Field testing of conversion of sewage sludge to daily landfill cover material

Solidification of sewage sludge has been actively investigated in Japan and Europe since the 1970s. Most previous studies have focused on only the mechanical aspects of potential alternative cover soil made using sewage. Most solidification processes, however, suffer from severe odor problems because of the high alkalinity of the material. The objectives of this study are to develop a cost-effective solidifying agent for conversion of sewage sludge in order to reduce the odor generation, as an alternative to the conventional cement lime-based solidifying agent, and to demonstrate its applicability in the field experimentally. Field test results showed compressive strength well above the 1.0 kg/cm² criterion for landfill cover soil in Korea. Also, the permeability coefficient was far below the 5 × 10⁻⁵ cm/s design criterion for landfill cover soil. Even in harsh weather conditions, such as in winter and summer, the compressive strength was increased. In addition, the permeability was decreased from 3.45 × 10⁻⁶ cm/s to 4.78 × 10⁻⁷ cm/s, and from 2.27 × 10⁻⁶ cm/s to 3.62 × 10⁻⁷ cm/s, at 7 days after placement in January and August, respectively. It can therefore be postulated that the proposed solidification process is an appropriate alternative for production of daily landfill cover material. Concerning the odor problem, 5 min of mixing of sewage with TS103, one of the proprietary agents used in this work, was sufficient to suppress the concentration of ammonia emitted to below 10 ppm. Considering all of these experimental field test results, it is expected that the proposed method could be a competitive approach for manufacture of alternative landfill cover material.     

Lactic acid production with undefined mixed culture fermentation of potato peel waste

Potato peel waste (PPW) as zero value byproduct generated from food processing plant contains a large quantity of starch, non-starch polysaccharide, lignin, protein, and lipid. PPW as one promising carbon source can be managed and utilized to value added bioproducts through a simple fermentation process using undefined mixed cultures inoculated from wastewater treatment plant sludge. A series of non-pH controlled batch fermentations under different conditions such as pretreatment process, enzymatic hydrolysis, temperature, and solids loading were studied. Lactic acid (LA) was the major product, followed by acetic acid (AA) and ethanol under fermentation conditions without the presence of added hydrolytic enzymes. The maximum yields of LA, AA, and ethanol were respectively, 0.22 g g^?1, 0.06 g g^?1, and 0.05 g g^?1. The highest LA concentration of 14.7 g L^?1 was obtained from a bioreactor with initial solids loading of 60 g L^?1 at 35 °C.     

Sedimentary Record of Polycyclic Aromatic Hydrocarbons in the Gulf of Trieste (Northern Adriatic Sea)

To reconstruct a history of polycyclic aromatic hydrocarbon (PAH) pollution in the Gulf of Trieste, one of the largest urbanized areas in the Adriatic Sea, we analyzed three long sediment cores collected between 1996 and 1997. Concentrations of total PAHs, the sum of 16 PAH compounds and six of their methylated analogues, in all three cores show a decrease from 600–800 ng g⁻¹, at the surface, to levels below 250 ng g⁻¹ in deepest layers (down to 3 m). The same trend was shown with separate representative pyrogenic PAHs (pyrene, benzofluoranthene and phenanthrene). Using Hg as a recent geochronological tracer, we observe an increasing input of PAHs since the beginning of the 20th Century and, especially, after the Second World War coinciding with increasing industrialization and urbanization of the region. This correlation is supported by PAH ratios that are indication of combustion processes and represent a marker for anthropogenic inputs. No correlation exists between PAHs and black carbon within the core profiles, indicating two different fractions of the ‘black carbon continuum’.     

Catalytic conversion of waste tyres into valuable hydrocarbons

Tyre recycling has become a necessity because of the huge piles of tyres that represent a threat to the environment. The used tyres represent a source of energy and valuable chemical products. Waste tyres were pyrolysed catalytically in a batch reactor under atmospheric pressure. Calcium carbide was used as a catalyst to explore its effect on pyrolysis product distribution. The effect of temperature, amount of catalyst and time on the yields of the pyrolysed products was investigated. Char yield decreased with increase of pyrolysis temperature while total gas and liquid yields increased. The liquid fraction was obtained with boiling point up to 320 °C. The physical and chemical properties of the pyrolysed products obtained were characterized. The catalytic pyrolysis produced 45 wt.% aromatic, 35 wt.% aliphatic and 20 wt.% of polar hydrocarbons. The distillation data showed that ∼80% of oil has boiling point below 270 °C which is the boiling point for 50% of distilled product in commercial diesel oil. The oil fraction was found to have high gross calorific value; GCV (42.8 MJ kg⁻¹). Its Specific gravity, viscosity, Kinematic viscosity, freezing point and diesel index were also within the limits of diesel fuel. The char residues were studied to investigate their characteristics for use as a possible adsorbent. Surface area of char before and after acid demineralization was determined to determine the adsorptive features for waste water treatment.