Experimental and numerical calculations of waste R-134a thermal decomposition for energy and fluorine material recovery

Considering the global warming potential of R-134a (C₂H₂F₄) with the substantial generation of this refrigerant as waste material in various industrial sectors, the development of proper thermal destruction method of R-134a is of great practical significance. For this, experiment and numerical calculations have initially made for a tubular-type furnace in order to figure out the basic combustion characteristics of R-134a. A series of experimental investigations for the thermal decomposition of R-134a have been made as a function of wall temperature of tubular furnace and important reacting species such as O₂ and H₂O necessary for the decomposition of C₂H₂F₄ into HF, CO₂ and H₂O. In general, the thermal decomposition of R-134a is successfully made for the condition of temperature above 800 °C with the supply of stoichiometric amount of O₂ and these results are well agreed with numerical prediction. And this information is employed for the simulation of a full-scale, practical incinerator used for the CDM project. For this, numerical investigation has been made for a commercial-scale incinerator using CH₄–air flames for the proper destruction C₂H₂F₄ together with the control of pollutants such as CO and NO. In general, the destruction rate of C₂H₂F₄ appears more than 99.99 % and the generation of CO and NO species appears rather sensitive to the operational condition such as amount of water vapor. The numerical method of HFCs (hydrofluorocarbons) thermal treatment shows high possibility as a viable tool for the proper design and optimal determination of the operational condition for a HFCs incinerator.     

Correction Factors for Covariance between Concentration and Deposition Velocity on CASTNes HNO3 Deposition Estimates

The covariance between hourly concentration (C) and depositionvelocity (V) for various atmospheric species may act to bias the dry deposition (D) computed from the product of the weeklyaverage C and V. This is a potential problem for the CASTNet filter pack (FP) species, nitric acid (HNO₃). Using ozone (O₃) behavior as a surrogate for HNO₃, correctionfactors (CF) are developed to estimate this bias. Weekly CF for O₃ depend on both site and season, and seasonal average weekly CF for O₃ at a given site may be as high as 1.25.The seasonal magnitude of this CF is generally largest in summerand is ordered: summer fall spring > winter. The CF is drivento a large extent by the diurnal correlation between C andV (i.e., both are generally higher during the day and lower at night). However, since the diurnal C profile at elevated sites is relatively constant, the resulting correlation between C and V is small, and the CF at montane sites is generally negligiblysmall. The sampling protocol using daytime integrated sampling for a week and nighttime integrated sampling for a week capturesthe diurnal correlation between C and V adequately and may be used to aggregate relatively unbiased weekly D estimates. Day-night CF for O₃ are close to unity, and limited results suggest similar behavior for HNO₃. Using these limited FP results, the site- and seasonally-specific weekly CF forO₃are refined to estimate the corresponding CF for HNO₃. Worst-case adjustments for HNO₃ as high as 30% are indicated for summer periods at a given site.     

Ammonium removal from landfill leachate by chemical precipitation

The landfill leachate in Hong Kong usually contains quite high NH₄⁺–N concentration, which is well known to inhibit nitrification in biological treatment processes. A common pre-treatment for reducing high strength of ammonium (NH₄⁺–N) is by an air-stripping process. However, there are some operational problems such as carbonate scaling in the process of stripping. For this reason, some technical alternatives for NH₄⁺–N removal from leachate need to be studied. In this study, a bench-scale experiment was initiated to investigate the feasibility of selectively precipitating NH₄⁺–N in the leachate collected from a local landfill in Hong Kong as magnesium ammonium phosphate (MAP). In the experiment, three combinations of chemicals, MgCl₂·6H₂O+Na₂HPO₄·12H₂O, MgO+85% H₃PO₄, and Ca(H₂PO₄)₂·H₂O+MgSO₄·7H₂O, were used with the different stoichiometric ratios to generate the MAP precipitate effectively. The results indicated that NH₄⁺–N contained in the leachate could be quickly reduced from 5618 to 112 mg/l within 15 min, when MgCl₂·6H₂O and Na₂HPO₄·12H₂O were applied with a Mg²⁺:NH₄⁺:PO₄³⁻ mol ratio of 1:1:1. The pH range of the minimum MAP solubility was discovered to be between 8.5 and 9.0. Attention should be given to the high salinity formed in the treated leachate by using MgCl₂·6H₂O and Na₂HPO₄·12H₂O, which may affect microbial activity in the following biological treatment processes. The other two combinations of chemicals [MgO+85% H₃PO₄ and Ca(H₂PO₄)2·H₂O+MgSO₄·7H₂O] could minimise salinity after precipitation, but they were less efficient for NH₄⁺–N removal, compared with MgCl₂·6H₂O and Na₂HPO₄·12H₂O. COD had no significant reduction during this precipitation. It was found that the sludge of MAP generated was easily settled within 10 min to reach its solids content up to 27%. The other characteristics including capillary suction time (CST) and dry density (DD) of the MAP sludge were also tested. The experimental results indicate that the settled sludge is quite solid and can be directly dumped at a landfill site even without any further dewatering treatment.     

Clean Preparation Process of Chitosan Oligomers in Gly Series Ionic Liquids Homogeneous System

Chitosan oligomers because of its water solubility has some special physiological functions, such as binding lipid, affecting the mitogenic response, restraining the growth of tumors, and was widely used in cosmetics and health. H₂O₂/Gly (Glycine) series ionic liquids system, a new solvable-catalytic system, was an efficient clean process for preparation of chitosan oligomers. The effects of the anions of Gly series ionic liquids on the solubility and degradation for chitosan were investigated, and the results showed that [Gly]Cl aqueous solution was of good solubility and assistant degradation for chitosan. In additional, the mechanism for oxidative degradation of chitosan in ionic liquids (ILs) was studied. The effect on the property of chitosan oligomers catalyzed by H₂O₂, in two different kinds of solvents (HAc and [Gly]Cl) were compared. It was found that the performance of moisture absorption and retention of chitosan oligomers using ionic liquid aqueous solution as solvent was better than that using HAc aqueous solution as solvent, and even superior to that of hyaluronic acid. Furthermore, [Gly]Cl could be easily separated from the product and reused with only slight loss. It could provide an efficient and environmental friendly method for the preparation of chitosan oligomers in H₂O₂/ILs system.     

Investigating the Use of Iron Reducing Bacteria for the Removal of Arsenic from Contaminated Soils

Clean-up techniques, which were developed for removing cationic heavy metals from contaminated soils, are inappropriate for the metalloid As, which is a common and highly toxic pollutant. Because arsenic is mainly found associated with the hydrous ferric oxides of the soil, a possible mechanism for the mobilisation of this element is the reductive dissolution of Fe(III) oxyhydroxides. In this paper we investigate the possibility to mobilise arsenic, using the Fe(III)-reducing bacterium Desulfuromonas Palmitatis. The initial experiments were carried out using a crystalline ferric arsenate as model compound, i.e. scorodite (FeAsO₄.2H₂O). D. palmitatis was found able to reduce the trivalent iron of scorodite at a percentage of 80% within 16 days, but arsenic remained in the pentavalent state, and reprecipitated with Fe(II) in the form of low solubility ferrous arsenates. To avoid the precipitation of ferrous arsenates the subsequent experiments with soil were conducted by combining the reducing ability of D. palmitatis with the chelating strength of EDTA (ethylenediamine tetracetic acid), which can form strong aqueous complexes with Fe(II). Approximately 60% of Fe and 75% of As were recovered in the aqueous solution in the presence of EDTA, while in the simple biological treatment no Fe was dissolved and only a 3% of As was mobilised.     

Heavy metals in wastewater: Modelling the hydroxide precipitation of copper(II) from wastewater using lime as the precipitant

The effect of effluent composition (Cl⁻, SO₄²⁻ or CO₃²⁻) on the efficiency of the hydroxide precipitation of Cu(II) modelling lime (CaO) as the precipitant has been predicted using the solubility domain approach and has been experimentally validated. Solubility domains were based on the phases that were found to be solubility-limiting for systems representing potential effluent chemical composition limits. The generated solubility domains generally encompassed the experimentally observed solubilities, thereby providing effluent treatment quality assurance ranges for the hydroxide precipitation process. The presence of gypsum (CaSO₄.2H₂O) and calcite (CaCO₃) as secondary precipitates had little effect on the observed residual Cu(II) solubilities, with Cu(II) mobility being governed by the least-soluble kinetically precipitated (rather than thermodynamically favoured) phase in the system under study.     

Neutralisation of Sulphur Dioxide Deposition in a Coniferous Canopy

Previously, it has been observed that the internal circulation (ion leakage) of calcium from a coniferous forest is caused by uptake of sulphur dioxide (SO₂). Here we show that this correlation was not changed when the forest floor is covered with a roof. The reaction takes place in the canopy and is not influenced by deposition and root uptake of calcium and sulphate. The ion leakage of calcium is linked to the loss of acidity in throughfall. The process can, for one of the catchments, schematically be written: SO₂ + H₂O + 0.5 O₂ + 0.58 CaA₂→ SO₄ ^2- + 0.94 H⁺ + 0.58 Ca²⁺ + 1.16 HA, in which A denotes the anion to a weak acid. This reaction also takes place today when the SO₂ concentration is very low, but when the precipitation is still acidic. The ion leakage of manganese also is caused by the uptake of SO₂, but only 0.12 manganese ions are released per SO₂ molecule.     

Water transport in polylactic acid (PLA), PLA/ polycaprolactone copolymers, and PLA/polyethylene glycol blends

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester, and water vapor permeability may have a significant influence on the rate of degradation. A method is devised to use bags prepared from PLA films and filled with molecular sieves to determine the water vapor permeability in the polymer, its copolymers with caprolactone, and blends with polyethylene glycol. The “solution-diffusion” model is used to determine the permeability parameters. These include the solubility coefficient,S, a measure of the equilibrium water concentration available for hydrolysis and the diffusion coefficient,D, which characterizes the rate of water vapor diffusion into the film under specific conditions. Values ofS andD at 50‡C and 90% relative humidity ranged from 400 × 10^-6 to 1000 × 10^-6 cm³ (STP)/(cm³ Pa) and 0.20 × 10^-6 to 1.0 × 10^-6 cm²/s, respectively. TheS andD coefficients were also measured at 20 and 40‡C and compared to those of other polymers. The degree of crystallinity was found to have little influence on the measured permeability parameters. The heat of sorption, δH_S, and the activation energy of diffusion, E_D, were used to show that the permeability process is best described by the “water cluster” model for hydrophobic polymers. Finally, the diffusion coefficient is used to compare the rate of water diffusion to the rate of water consumption by ester hydrolysis. Results indicate that hydrolytic degradation of PLA is reaction-controlled.     

Extracellular Biopolymer Production by Aureobasidium pullulans MTCC 2195 Using Jackfruit Seed Powder

In this present paper, statistical screening and optimization of jackfruit seed powder based medium components were investigated for pullulan production from Aureobasidium pullulans. Seven medium variables jackfruit seed powder, K₂HPO₄, yeast extract, (NH₄)₂SO₄, NaCl, MgSO₄·7H₂O and ZnSO₄·7H₂O were screened by employing Plackett–Burman (PB) method. PB method showed jackfruit seed powder, ZnSO₄·7H₂O, K₂HPO₄ and yeast extract were significant. Central composite design of response surface method applied to optimize the significant variables identified from the PB experiment. Statistical analysis of the experimental results showed optimal values were found to be jackfruit seed powder 2 % (w/v), K₂HPO₄ 0.55 % (w/v), yeast extract 0.30 % (w/v) and ZnSO₄·7H₂O 0.006 % (w/v) with maximum pullulan concentration of 18.76 (g/L). Maximum pullulan concentration of 17.95 (g/L) was observed in the validation experiment. This experimental result explained the model was fitted 96 % as compare with the result predicted by response surface method.     

Active Bio-composite Sodium Alginate/Maltodextrin Packaging Films for Food Containing Azolla pinnata Leaves Extract as Natural Antioxidant

The aim of the current work was to produce sodium alginate (SA) maltodextrins (MD) based functional films incorporated with phenolic extract of Azolla pinnata leaves fern (AF) by solution molding technique. AF with different concentrations (0.8, 1.2 and 1.6% w/w) were integrated inside SA.MD films. The resulted films were characterized to investigate the surface structure by scanning electron microscope (SEM), thermal disposal by (DSC), crystallization by X-ray diffraction (XRD), potential interaction by (FT-IR) and some mechanical properties. The SEM micrographs indicated that the higher concentration (1.6%) of AF extract caused development of wrinkles on the surface of films. And as a result, there were a significant decrease of elongation at break (EB) and tensile strength properties of films to 55.01 and 58.42%, respectively. By continues addition of AF extract to SA.MD films, the film thickness increased from 0.124 to 0.181 mm, the scavenging and antimicrobial properties were enhanced by the attendance of ferulic acid, rutin, thiamine, tamarixetin, astragalin, quercetin, chlorogenic acid and epicatechin inside extracts. Furthermore, the films solubility, swelling degree and water vapor permeability were decreased to 13.08%, 26.41% and 1.662?×?10^??10 g H₂O/m s p.a. The resulted films could be utilized as composite packaging material for different food applications.

     

Nucleophilic substitution of poly(vinyl chloride) with iminoacetic acid and n-dodecanethiol

The modification of poly(vinyl chloride) was carried out with iminodiacetic acid (IDA, C₄H₇NO₄) and iminodiacetic acid dimethylester (IDADM, C₆H₁₁NO₄), as well as with n-dodecanethiol (DT, C₁₂H₂₆S) in the presence of K₂CO₃. The reaction was carried out at different temperatures below 100 °C with dimethyl formamide (DMF) and cyclohexanone as solvents. IDA did not show any reactivity, probably due to the dipolar character of the molecule. IDADM caused the elimination of HCl, while only substitution ratios of about 3 % were observed. However, the modification of PVC with DT resulted in a substitution rate of 18 % without elimination. DT-PVC showed excellent thermal properties, comparable with those of the unmodified polymer.     

Nitrous oxide emission from some English and Welsh rivers and estuaries

Nutrient and N₂O concentrations in the water columns were measured seasonally over a full salinity range in the nutrified rivers Colne, Stour, Orwell, Deben, Trent, Ouse and Humber and their estuaries on the east coast of England between August 2001 and May 2002, and in the oligotrophic rivers Conwy, Dovey and Mawddach in North and West Wales between August 2002 and May 2003. Nutrient and N₂O concentrations in the nutrified English rivers and estuaries were much higher than those in the Welsh rivers. N₂O concentrations and % saturation in the estuaries were significantly correlated with nitrate, nitrite and ammonium concentrations in the water. The strongest correlation was with nitrite (r² = 0.56, p < 0.01), suggesting that nitrite was the most significant factor among the different nutrients in regulating N₂O concentration in the estuaries. N₂O concentrations in the English rivers and estuaries were supersaturated throughout the year with annual averages from 186.9 to 992.9%, indicating that these rivers and estuaries were sources of atmospheric N₂O, whereas in the Welsh rivers N₂O concentrations were much lower with annual averages from 113.6 to 137.4% saturation. Although the estuarine area in the Colne was almost the same as that in the Conwy, the annual N₂O emission from the Colne was much higher (937498 mol N yr^–1) than in the Conwy (23020 mol N yr^–1). On the east coast, riverine emissions of N₂O were only 0.5–12.5% of the total emission from rivers and estuaries. Thus rivers were negligible, but estuaries were significant contributors to the UK N₂O inventory.     

Ozone Dry Deposition Velocities for Coastal Waters

Air-sea exchange rates for ozone were measured by the eddy correlation technique at a site on the north Norfolk coast in the UK. The average surface resistance to ozone uptake was found to be, r_s(O₃) = 1,000 ± 100 s m^-1. Micrometeorological measurements of trace gas fluxes to ocean surfaces are rare but a review of available measurements suggests that we can constrain sea water surface resistance for ozone to between 1,000 (Regener (1974), and this work) and 1,890 s m^-1 (Lenschow et al., 1982), yielding surface deposition velocities between 0.53 and 1.0 mm s^-1. These values are more than an order of magnitude greater than can be explained by laboratory determined mass accommodation coefficients for ozone to water. The importance of dry deposition with respect to process air-sea exchange models is highlighted. A trend in surface deposition velocity with wind speed was also observed supporting a surface chemical enhancement mechanism of ozone uptake which in turn is enhanced by near surface mixing processes.     

Organoclays for Aquifer Bioremediation: Adsorption of Chlorobenzene on Organoclays and its Degradation by RHODOCOCCUS B528

The adsorption and degradation of chlorobenzene on partially modified organoclays and by the autochthonous microorganism Rhodococcus B528 were studied by means of the batch technique. Organoclays were prepared from Na-montmorillonite (MM) by using dodecyltrimethylammonium (C₁₂) and dioctadecyldimethylammonium (2C₁₈) bromides. The degree of modification was 35 (2C₁₈-35-MM) and 89% (C₁₂-89-MM) of the cation exchange capacity of MM. The adsorption experiments were carried out using headspace GC. The intercalation of chlorobenzene into the interlayers of organo-MM was detected by X-ray diffraction. The adsorption isotherms found were of the S1 type indicating a cooperative effect. Chlorobenzene showed a higher affinity for 2C₁₈-35-MM than C₁₂-89-MM, which could not only be explained by the organic carbon content. The comparison with 2,4-dichlorophenol adsorption has implied that for the studied systems the different adsorption mechanisms are primarily governed by the different molecular properties and not by the type of absorbent. The presence of 2C₁₈-35-MM caused no negative effect on the investigated microorganisms and complete biodegradation of chlorobenzene was achieved without desorption limitation for growth, demonstrating the applicability of partially modified organoclays for bioremediation.     

Adsorption of Geosmin and MIB on Activated Carbon Fibers–Single and Binary Solute System

The adsorption of two taste- and odor-causing compounds, namely MIB (2-methyl isoborneol—C₁₁H₂₀O) and geosmin (C₁₂H₂₂O) on activated carbon was investigated in this study. The impact of adsorbent pore size distribution on adsorption of MIB and geosmin was evaluated through single solute and multicomponent adsorption of these compounds on three types of activated carbon fibers (ACFs) and one granular activated carbon (GAC). The ACFs (ACC-15, ACC-20, and ACC-25) with different degrees of activation had narrow pore size distributions and specific critical pore diameters whereas the GAC (F-400) had a wider pore size distribution and lesser microporosity. The effect of the presence of natural organic matter (NOM) on MIB and geosmin adsorption was also studied for both the single solute and binary systems. The Myers equation was used to evaluate the single solute isotherms as it converges to Henry’s law at low coverage and also serves as an input for predicting multicomponent adsorption. The single solute adsorption isotherms fit the Myers equation well and pore size distribution significantly influenced adsorption on the ACFs and GAC. The ideal adsorbed solute theory (IAST), which is a well-established thermodynamic model for multicomponent adsorption, was used to predict the binary adsorption of MIB and geosmin. The IAST predicted well the binary adsorption on the ACFs and GAC. Binary adsorption isotherms were also conducted in the presence of oxygen (oxic) and absence of oxygen (anoxic). There were no significant differences in the binary isotherm between the oxic and anoxic conditions, indicating that adsorption was purely through physical adsorption and no oligomerization was taking place. Binary adsorptions for the four adsorbents were also conducted in the presence of humic acid to determine the effect of NOM and to compare with IAST predictions. The presence of NOM interestingly resulted in deviation from IAST behavior in case of two adsorbents, ACC-15 and F-400.     

Nitrous Oxide Emissions from Two Riparian Ecosystems: Key Controlling Variables

Nitrous oxide (N₂O) emissions were measured weekly to fortnightly between April 2001 and March 2002 from two riparian ecosystems drainingdifferent agricultural fields. The fields differed in the nature of the crop grown and the amount of fertiliser applied. Soil water content and soil temperature were very important controls of N₂O emission rates, with a ‘threshold’ response at 24% moisture content (by volume) and 8 °C, below which N₂O emission was very low.N₂O fluxes were higher at the site that had receivedthe most fertiliser N, but NO₃ ^- was not a limiting factor at either site. There was also a ‘threshold’ effect of rainfall, in which major rainfall events (≥10 mm) triggered a pulse of high N₂O emission if none of the other environmental factors were limiting. These results suggest the existence of multiple controls on N₂O emissions operating at a range of spatial and temporal scales and that non-linear relationships, perhaps with a hierarchical structure, are needed to model these emissions from riparian ecosystems.     

Mechanochemical dechlorination of polyvinyl chloride with calcium sulfates

Polyvinyl chloride (PVC) was milled with hydrated or unhydrated calcium sulfates (CaSO₄·2H₂O or CaSO₄) in air by using a planetary mill to investigate mechanochemical dechlorination behavior. The milling process resulted in size reduction and in the breaking of bonds leading to mechanically induced solid state reaction, forming CaCl₂ and dechlorinated hydrocarbon with C=C double bonds in the product. Washing the milled mixtures with water at room temperature allowed removal of the chloride formed during milling, and more than 95% of the chlorine in PVC was removed from a mixture milled for 4 h. This process could offer a potential route for the handling and disposal of both PVC and gypsum wastes. H₂S gas was generated during milling; more H₂S was released from the unhydrated sample than from the hydrated sample.     

Groundwater treatment and aquatic toxicity reduction at a chemical production site

Contaminated groundwater at a chemical antioxidant and phenolic resin chemical production site was subjected to treatability studies to develop design criteria for surface water discharge. Raw groundwater required pretreatment for total suspended solids (TSS) and color removal prior to treatment by ultraviolet light/hydrogen peroxide (UV/H₂O₂). Because of high capital and operating costs for UV/H₂O₂, biological treatment was evaluated as an alternate. Respirometric analyses showed that completely mixed activated sludge could be applied as a treatment technology to the groundwater. Biotreatment resulted in an approximately 70 percent reduction in soluble chemical oxygen demand (SCOD). Residual SCOD was recalcitrant to further biodegradation. The treated effluent was tested for aquatic toxicity using fathead minnows (Pimephales promelas) and Ceriodaphnia dubia and was found to be toxic. Toxicity reduction of biotreatment effluent was evaluated in bench-scale experiments using activated carbon adsorption, filtration, and UV/H₂O₂. Subsequent toxicity testing showed that filtration alone could reduce the bioeffluent toxicity and that residual SCOD was not the primary source of toxicity.     

Kinetic and Mechanistic Studies of NO X Selective Catalytic Reduction Over In/Al2O3 and N2O Decomposition Over Ru/Al2O3

Detailed kinetic studies are presented for two reactions: the nitric oxide (NO) selective catalytic reduction (SCR) by propene over indium/alumina (In/Al₂O₃) and the nitrous oxide (N₂O) reduction over ruthenium/alumina (Ru/Al₂O₃). Both reactions were studied in the presence of excess oxygen (O₂) to simulate the composition of flue gases. Apparent activation energies and apparent orders of reaction were calculated in experiments performed under differential reaction conditions. We used our experimental results to propose the reaction mechanism that leads to nitrogen formation over the two catalysts. The NO reduction proceeds through the initial formation of C _X H _Y O _Z N, a reaction intermediate that reacts with activated nitrogen oxides (NO _X ). Nitrous oxide is catalytically decomposed to nitrogen (N₂) over Ru/Al₂O₃.     

The behaviors of H2, CH4, C2H4 and C3H6 from the decomposition of polypropylene by NiO/Si–Al catalyst

The purpose of this study was to investigate the possibility of light gases produced from polypropylene, specifically hydrogen. In particular, we examined the effect of operating conditions on gaseous product and compositions in the catalytic cracking of polypropylene. We also characterized the gaseous product generated from polypropylene cracking. The feedstock (2.0 g) mixed with NiO/SiO₂–Al₂O₃ (Si–Al) was used, under non-isothermal conditions at low temperature range between 380 and 500 °C. Argon gas was used to carry the pyrolyzed gas, and the gas collected in a tedlar bag was analyzed for its behavior. We observed the behavior of major gases (H₂, CH₄, C₂H₄ and C₃H₆, etc.) according to reaction time and temperature. Finally, the effect of reaction conditions on evolved gases from catalytic cracking of polypropylene was analyzed.