Ce travail concerne la mesure et la caractérisation du transfert thermique à la paroi externe d'un faisceau de tube de refroidissement inséré dans des colonnes à bulles type " slurry ". La valeur du coefficient de transfert de chaleur est estimée à partir des équations de la chaleur. Une colonne de 0,15 m de diamètre et de 4 m de haut, équipée de deux tubes en U (3 cm de diamètre externe), a été utilisée pour mettre au point la métrologie nécessaire. L'eau a servi de fluide de refroidissement. Le mélange diphasique air-huile Syltherm XLT®, puis le mélange triphasique air-huile Syltherm XLT®-microbilles d'alumine poreuses (dS ~ 80 μm), ont servi de fluides modèles. L'incertitude de nos mesures a été estimée à environ 8 %. En système diphasique, les variations du coefficient de transfert de chaleur avec la vitesse superficielle du gaz ont pu être corrélées par une loi semblable à celle de Deckwer (1980). Cependant, la valeur de la constante de corrélation semble dépendre de l'orientation du faisceau de tubes par rapport à l'axe de la colonne. Un tel comportement n'a jamais été rapporté dans la littérature. L'écart du faisceau à un faisceau idéal (i.e. parfaitement droit et symétrique) peut être un paramètre crucial pour le transfert de chaleur. En système triphasique, la valeur du coefficient ne varie pas de façon significative jusqu'à une concentration massique d'environ 18,8 %, avant de diminuer d'environ 10 % pour une concentration massique de 21,3 %. Ce résultat est surprenant. Les variations rapportées dans la littérature sont en effet souvent contradictoires, mais toujours continues dans la gamme de concentrations testée. La métrologie mise au point a été implantée dans une colonne de 1 m de diamètre et de 5 m de haut, équipée de 24 tubes en U (6 cm de diamètre externe). Celle-ci est jugée représentative d'un réacteur pour le procédé Fischer-Tropsch. Les premiers résultats indiquent que la caractérisation thermique de l'installation sera plus délicate que pour la petite colonne

Arsenic and selenium distributions in coal-fired plant samples are studied. This research includes arsenic and selenium concentrations in samples of coal, fly ash, bottom ash, economizer ash, Flue Gas Desulfurization (FGD) slurry and flue gas taken from four power plants with the goal being to examine the distribution of these metals in these materials and calculate a materials balance for the system. All samples were analyzed using ICP-ES. This research shows that 60-80% of the arsenic in coal-fired plant samples will be associated with the fly ash. Approximately 35-55% of the selenium will be associated with the fly ash and approximately 30-40% will be associated with the FGD slurry materials. The amount of arsenic and selenium present in the flue gases escaping the stack is very little, 6-7% or less. Hopefully, research in this area will be helpful when setting emissions limits, identifying and disposing of hazardous wastes and improving air pollution control devices for maximum metal removal.

Ammonia is a nuisance gas in many swine barns. The overall objective of this research project was to model ammonia formation and transmission processes in a grower-finisher swine barn, by first modelling the ammonia production and emission from urine puddles on the floor surface and the ammonia emission from the slurry pit, and then incorporating these emission rates in a dynamic model that separates the room and slurry pit headspace as two separate, but linked, control volumes. A series of studies were conducted to gather more information about the processes affecting the ammonia emission rate from the floor surface and the slurry that were later included in the overall room model developed. The model was then used to investigate ammonia reducing techniques and technologies based on the understanding of ammonia production and transmission incorporated in the model. The first step in modelling the ammonia emission rate from the floor surface was to determine the frequency of urinations by grower-finisher pigs. Male and female pigs were observed three times during their finishing phase to determine their urination frequency over the course of a day. The average measured urination frequency was 0.62 ± 0.11 urinations pig-1 h-1. A sinusoidal dromedary model was developed to describe the daily variation in urination frequency for male and female pigs between 51 and 78 kg.<p>In order for the deposited urinations on the floor surface to emit ammonia, the urea in the urine must first be converted to ammonia and the urease enzyme catalyzes this reaction. Two methods, a fixed-time-point method using the indophenol assay for ammonium-nitrogen analysis and a continuous method using the coupled enzyme assay, were used to measure enzyme activity at the floor surface of a swine barn and were compared to reported urease activity levels in the literature. Using both methods, there appeared to be an ammonia-producing site on the floor surface or within the collected samples that made accurate measurements of urease activity impossible. A review of urease activity levels in the literature from dairy-cow houses suggest that urease activity will be lowest following floor-cleaning and increase quickly following fouling of the floor surface. Based on the literature review, a urease activity value of 5 g NH¬3 m-2 h-1 was suggested for use in ammonia emission modelling of fouled floor surfaces in swine barns until better measurements become available. <p>The ammonia emissions from 36 simulated urine puddles under a variety of temperature, air velocity and initial urea concentration conditions were measured in a bench-scale experimental set-up. The measurements were used to calibrate and validate a dynamic, mechanistic, urine puddle emission model that considered the processes of evaporation, urea conversion, change in liquid concentration and puddle pH in order to simulate the amount of ammonia emitted from a puddle. Based on the correlation coefficients (R) between measured and simulated values for water volume (R=0.99), total ammoniacal nitrogen concentration (R=0.90), and total emission (R=1.00), along with five other statistical tests for each simulated variable, the model was deemed accurate. The measurements and simulations in this experiment showed the impact of puddle pH, urease activity and changing environmental conditions on the average puddle emission rate. Puddle emission continued to occur as long as there was still water.<p> The impact of different slurry compositions on the ammonia emission rate from slurry pits was tested in another bench-scale experimental set-up with emission chambers. The emission chamber concentration data collected was used to calibrate and validate a developed slurry emission model. The collected slurry samples were concentrated mixtures of urine and feces from individually-housed animals fed different diets. An empirical equation was developed to express the amount of total ammoniacal nitrogen in the slurry that was in the form of ammonia (f) and thus volatile to the surroundings. Based on the empirical equation, the simulated value of f was between 0.03 and 0.08 and did not show the sensitivity to slurry pH that has been reported by other authors. The slurry emission model with the empirical equation for f was validated with ammonia emission measurements from eight different slurry samples and simulated hourly concentration measurements within 17% and five-day average concentration measurements within 3%. Further testing was recommended to ensure the model developed for concentrated manure in this study was applicable to the more dilute slurry found in swine barns. <p>Using the information gained in the previous experiments, a mechanistic model describing the dynamic ammonia concentration in the room and in the slurry channel headspace of grower-finisher swine barns, as well as the ammonia emitted to the surrounding environment was developed. Data was collected from two grower-finisher rooms to use as input data to the model and for calibration and validation purposes. The model calibration procedure determined that the amount of emissions originating from the slurry for the simulated room conditions was generally less than 5% of the total room emissions, the air exchange rate through the slatted floor was approximately 4% of the room ventilation rate, and that in the first two weeks of animal activity in a room the urease activity at the floor surface will increase. The model was validated using separate data from that used in the calibration process. The model simulated hourly room concentration levels within 2.2 ppm and 3-day average concentration levels within 1.6 ppm. The model simulations were more accurate for one room that was fed a typical grower-finisher diet compared to another room fed an experimental diet with lower protein content and sugar-beet pulp inclusion. <p>The dynamic model was tested for its sensitivity to various input factors in terms of the floor emission rate, slurry emission rate and total emission rate. An interesting aspect of the simulations was that increases in either floor or surface emission rate were compensated to a small extent by decreases in the other emission rate as a result of a reduced concentration gradient for mass transfer. The ammonia emission rate from the floor was most sensitive to changes in urease activity, fouled floor area and puddle area. The ammonia emission rate from slurry was most sensitive to changes in slurry pH. The impact of input variables on the total emission rate was dependant on the simulated proportion of the total ammonia emission coming from either the floor surface or slurry channel. Three ammonia reduction techniques were tested and evaluated on their impact to the total ammonia emission rate from a room compared to a given set of control conditions.<p>The work in this thesis highlighted the importance of ammonia emission from the floor surface. The proportion of ammonia originating from the slurry and from the floor surface respectively will vary on the specific conditions within the barn, and will impact the effect of any ammonia mitigation technique that is investigated or used.

No description available.

Abstract The object of this study was to investigate the synthesis of a nanoscale zero-valent iron slurry (NZVIS) for use in Fenton-like reactions, and to evaluate its efficiency for As(III) oxidation to As(V) in spiked deionized water and simulated groundwater containing humic acid. Furthermore, this study used injection of the nanoiron slurry combined with electrokinetic processes to remediate As(III) in soil. NZVI was prepared by a chemical reduction process. The efficiency of using 3 wt% soluble starch (SS) to stabilize NZVI was also studied. It was found that the SS could keep the nanoparticles dispersed for over one day. The NZVI was characterized by XRD, FE-SEM, ESEM-EDS, and EDS-mapping, to observe its morphology and crystal structure. In this research the iron species observed took non-crystalline forms. In water batch tests, studies in deionized water were compared with those in simulated groundwater with humic acid, and dissolved oxygen content was adjusted. Injection of NZVIS oxidized As(III) to As(V) in all cases. In both deionized water and simulated groundwater, it was found that when the dissolved oxygen(DO) content was not increased, the NZVIS generated non-selective oxidant OH¡E, thus reducing the As(V) production rate. When dissolved oxygen content was increased, the DO oxidized organic matter present in the simulated groundwater, allowing the OH¡E to react further with As(III) and increasing the As(V) production rate. Finally, a test was performed in actual groundwater under optimal reaction conditions, without increasing the dissolved oxygen content, for comparison of As(V) yield. The concentration of As(V) was found to be higher in this test (As(V) Conc. = 17.55 £gg/L) than when using simulated groundwater (As(V) Conc. = 4.63 £gg/L). This study further examined NZVIS injection combined with electrokinetic (EK) technology for the remediation of soil columns containing a low concentration (initial conc. = 100 mg/kg) and a high concentration (initial conc. = 500 mg/kg) of As(III). EK alone without injection of NZVIS (Test E-1) resulted in a residual soil As(V) concentration of 24 mg/kg in the low-concentration test group. In Test E-2, where NZVIS was injected into the anode reservoir, and Test E-3, where NZVIS was injected into the cathode reservoir, residual soil As(V) concentrations were 2.3 mg/kg and 3.4 mg/kg, respectively. The high-concentration test group was comprised of Test E-4 (EK alone without injection of NZVIS), Test E-5 (NZVIS injected into anode reservoir), and Test E-6 (NZVIS injected into cathode reservoir). In these tests, only soil sections 0.2 and 0.4 (normalized distance from anode reservoir) met soil regulation standards. Residual As(V) concentrations in soil sections 0.6, 0.8, and 1.0 are much higher than the regulatory standard. In soil section 1.0, the residual As(V) concentration was less in Test E-6 than in Test E-5 (116.6 mg/kg and 183.5 mg/kg, respectively). This may be because at high pH values, the iron surface does not corrode, instead arsenic adsorption prevails. Only a fraction of negatively charged As(V) species will migrate towards the anode resulting in a relatively low soil As(V) concentration near the cathode.

Leaking of petroleum products from storage tanks is a commonly found cause of soil contamination. Among those petroleum products, diesel-oil contaminated soils are more difficult to treat compared to gasoline (a more volatile petroleum product). With the growing interest in environmental remediation, various approaches have been proposed for treating petroleum-hydrocarbon (PH) contaminated sites. Given that it is often not possible to remove the released oil or remediate the site completely within a short period of time, using the in situ remedial technology, soil excavation followed by more cost-effective technology should be applied to accelerate the efficiency of site cleanup. In the first-part of this study, laboratory degradation experiments were conducted to determine the optimal operational conditions to effectively and economically bioremediate diesel-fuel contaminated soils. In the second part of this study, a combined full-scale landfarming and biopile system was operated to cleanup diesel fuel-contaminated soils. In the laboratory study, except of frequent soil tilling for air replacement, different additives were added in the laboratory bioreactors to enhance the total petroleum hydrocarbon (TPH) removal efficiency. The additives included nutrients, TPH-degrading bacteria, activated sludge, fern chips, and kitchen waste composts. PH-degrading bacteria were isolated from PH-contaminated soils and activated sludge was collected from a wastewater treatment plant containing PH in the influent. PH-degrading bacteria and sludge were added to increase the microbial population and diversity. Fern chips and kitchen waste composts were added to increase the soil permeability. Results indicate that the bioreactor with kitchen waste compost addition had the highest TPH removal rate. The observed TPH-removal ratios for the compost, activated sludge, PH-degrading bacteria, fern chips, nutrients, TPH-degrading bacteria addition, and control (with HgCl2 addition) groups were 80.5%, 78.6%, 77.4%, 75.1%, 73.3%, 66.1%, and 1.6% respectively. In the field study, activated sludge was selected as the additive from the engineering point of view. With the addition of activated sludge, an increase of 20% was observed for TPH removal ratio. Results from the denaturing gradient gel electrophoresis (DGGE) tests show that the detected PH-degrading bacteria in the activated sludge included the following: Pseudomonas sp., Pseudoxanthomonas sp., Rhodocyclaceae bacterium, Variovorax sp., Acidovorax sp., Leptothrix sp., Alcaligenaceae bacterium, and Burkholderia sp. Some of these bacteria became dominant species in the field after a long-term operation, which was beneficial to the soil bioremediation. Results indicate that the in situ bioremediation has the potential to be developed into an environmentally and economically acceptable remediation technology.

Ultrasonic slurry sampling electrothermal vaporization dynamic reaction cellTM inductively coupled plasma mass spectrometry (USS-ETV-DRC-ICP-MS) has been applied to determine Cr, Cu, Cd, Hg and Pb in several rice samples. The influences of instrument operating conditions and slurry preparation on the ion signals were reported. Ascorbic acid was used as the modifier to enhance the ion signals. The background ions at the chromium masses were reduced in intensity significantly by using 0.4 ml min-1 NH3 as reaction cell gas in the dynamic reaction cell (DRC) while a q value of 0.6 was used. Since the sensitivities of Cr, Cu, Cd, Hg and Pb in rice flour slurry and aqueous solution were quite different, standard addition and isotope dilution methods were used for the determination of Cr, Cu, Cd, Hg and Pb in these rice samples. This method has been applied to the determination of Cr, Cu, Cd, Hg and Pb in NIST SRM 1568a rice flour reference material and two rice samples purchased from the market. The analysis results of the reference material agreed with the certified values. The results for the rice samples for which no reference values were available were also found to be in good agreement between isotope dilution method and standard addition method. The method detection limits estimated from standard addition curves were about 0.44, 1.7, 0.4, 0.53 and 0.69 ng g-1 for Cr, Cu, Cd, Hg and Pb, respectively, in original rice flour.Ultrasonic slurry sampling electrothermal vaporization dynamic reaction cellTM inductively coupled plasma mass spectrometry (USS-ETV-DRC-ICP-MS) has been applied to the determination of Cr, Cd and Pb in several plastic samples. The influences of instrument operating conditions and slurry preparation on the ion signals were investigated. NH4NO3 was used as the modifier to enhance the ion signals. The background ions at the chromium masses were reduced in intensity significantly by using NH3 as reaction cell gas in the DRC. Standard addition method and isotope dilution method were used for the determination of Cr, Cd and Pb in these plastic samples. This method was applied to the determination of Cr, Cd and Pb in two polystyrene and a polyvinyl chloride samples. The analysis results were found to be in good agreement between isotope dilution method and standard addition method. Furthermore, we digested these samples and analyzed the digested sample solutions by ultrasonic nebulization DRC ICP-MS. The analysis results were close to the isotope dilution and standard addition results. The precision between sample replicates was better than 3% with USS-ETV-DRC-ICP-MS method. The method detection limits estimated from standard addition curves were about 6.2-9.2, 1.1-1.6 and 8.4-11 ng g-1 for Cr, Cd and Pb, respectively, in original plastic samples.

Air pollution by sulfur dioxide is of great concern due to its harmful effects on environment, human beings, fauna and flora. Fossil-fuel-fired power plants are one of the major sources of SO2 emissions. Typically the concentration of SO2 in the flue gases of these plants is in the range of 2000 to 20000 ppm. Flue gas desulfurisation is one of the widely practiced strategies to control SO2 emissions. Aqueous phase oxidation of sulfur dioxide catalysed by carbonaceous particles is an attractive alternative to the conventional processes for flue gas desulfurisation because, amongst other reasons, sulfuric acid, the product of aqueous phase oxidation, finds extensive application in industry. In the literature it has been reported that sulfuric acid affects the solubility of sulfur dioxide and that activated carbon catalyses aqueous phase oxidation. However there is hardly any report on the systematic evaluation of the mechanism of the heterogeneous aqueous phase oxidation of sulfur dioxide which takes into account among other factors, the effect of sulfuric acid on the solubility of SO2 (particularly, at low levels of SO2 and sulfuric acid concentrations). Therefore the objective of the present work is to evaluate systematically the aqueous phase oxidation of SO2 in ppm levels with activated carbon as catalyst in a three-phase agitated slurry reactor and to model rigorously the solubility of SO2 in ppm levels in dilute sulfuric acid solutions and to estimate the concerned parameters experimentally. Strong effect of dilute concentrations of sulfuric acid on the solubility of SO2 is analyzed in terms of the influence of the acid on the equilibrium concentrations of the ionic species (HSO3¯ and SO4¯2 formed from the hydrolysis of SO2 (aq) and the dissociation of H2SO4 respectively) in SO2 - dil. H2SO4 systems. The analysis leads to a general expression relating the partial pressure of SO2 in the gas phase to the concentration of total dissolved SO2 and the concentration of sulfuric acid in the solution. Simple equations are obtained from the general expression for the cases of zero and high concentrations of sulfuric acid in the system, which in turn lead to direct experimental determination of the parameters, Henry's law constant and the equilibrium constant of hydrolysis of SO2 (aq). The developed model predicts the present experimental data as well as the data reported in the literature very closely. The dissolution of SO2, the hydrolysis of SO2 (aq) and the dissociation of H2SO4 are found to be instantaneous. From the dependency of the parameters on temperature, the heat of dissolution of SO2 is determined to be -31.47 kJ mol"1 and the heat of hydrolysis to be 15.69 kJ mol"1. The overall heat of solubility of sulfur dioxide is therefore -15.78 kJ mol"1. Preliminary reaction experiments have clearly indicated that SO2 (aq) does not react and HSO3¯ is the only reactant for aqueous phase oxidation of sulfur dioxide catalysed by activated carbon. The non-reactant SO2 (aq) deactivates the oxidation reaction by competing with HSO3¯ for adsorption on the active sites of the catalyst particles. However the catalyst particles become saturated with SO2 (aq) beyond a certain value of its concentration (saturation limit), which depends on temperature. A mechanism is proposed based on these observations to develop a rate model. The rate model also takes into account the effect of the concentration of the product sulfuric acid on the solubility of sulfur dioxide. The model predicts first order in HSO3¯ , half order in dissolved oxygen and a linear deactivation effect of 5O2(ag). The oxidation reaction is evaluated experimentally at various levels of the operating variables such as temperature and the concentrations of sulfur dioxide and oxygen in the inlet gas. In all experiments a pseudo steady-state region is observed where the gas phase concentration of SO2 reaches a steady value but the concentrations of HSO3¯ and total S (VI) in the liquid phase continue to change. Pseudo steady-state considerations lead to the determination of the initial estimates of the parameters of the rate model namely, the rate constant and the deactivation constant. These parameters are estimated from the transient profiles of the product (sulfuric acid) by solving the model equations by Runge-Kutta method along with Marquardt's non-linear parameter estimation algorithm. The predictions of the model with the estimated parameters match very well with the experimentally observed concentration profiles of S(VI) and HSO3 in the liquid phase and SO2 in the gas phase. The deactivation constant in the saturation range is independent of temperature and is 0.27, which indicates that the intrinsic rate constant is about four times greater than the observed rate constant. From Arrhenius equation-type dependency of the parameters on temperature, the activation energy for the oxidation reaction is determined to be 93.55 kJ mol"1 and for deactivation to be 21.4 kJ mol"1. The low value of activation energy for deactivation suggests a weak dependency of the deactivation on temperature, which perhaps is due to the weak nature of the chemisorption of SO2 (aq) on carbon.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1951. / Includes bibliographical references (p. 117-119).

In the modern semiconductor manufacturing processes, chemical mechanical planarization (CMP) has attained important processing step because of its ability to provide global planarization. CMP is the planarization technique which is used for the removal of excess material, as left over from the previous processing steps. In addition, CMP offers a uniform surface that is essential for subsequent processing steps, especially for the high resolution photolithography processes. In simpler notation, CMP is a process where a chemical reaction enhances in obtaining a planar surface through removal of the mechanical materials from a wafer. In this study, CMP performance of three electronic materials was investigated. Chemical vapor deposited (CVD) diamond films, as a first materials, was fabricated using hot-filament chemical vapor deposition technique (HFCVD). The synthesized microcrystalline diamond (MCD) films were characterized using Raman Spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), and X-ray Diffraction (XRD). The CMP performance of the MCD and nanocrystalline diamond (NCD) synthesized in Nano Materials Research Laboratory (NMRL) were investigated by using commercial slurry procured by Logitech Inc. U.K. The post-CMP characterizations of diamond films were performed by AFM in order to investigate surface roughness. The result showed the significant reduction the surface roughness of MCD films (37 nm to 15 nm) and NCD films (18 nm to 12 nm). In addition, the CMP performance of the silicon dioxide was investigated in this research work. The novel nanodiamond-polymer based slurry was also developed by co-polymerization of N-isopropylacrylamide (NIPAM) and N,N'-methylenebisacrylamide, 3-(trimethoxysilyl) propyl methacrylate (MPS). The synthesized slurry was characterized by Transmission Electron Microscopy (TEM) for observing the dispersion of diamond particles in the polymer matrix. The investigation of silicon dioxide was carried out using conventional ceria based slurry and novel nanodiamond-polymer based slurry. The results showed excellent surface finish at the minor expense of material removal rate with nanodiamond-polymer based slurry. Also, the coefficient of friction of friction was significantly reduced by using novel nanodiamond polymer based slurry. Lastly, CMP behavior of copper wafer was examined under different polishing conditions. The polishing was carried out using the commercial slurry procured from Cabot Microelectronics Inc., U.S. The copper wafers were characterized by AFM in order to analyze surface roughness. The results showed the reduction in average surface roughness occurred from 4.7 nm to 1.7 nm. This range of average surface roughness meets the demands of modern semiconductor industries.