ABSRACT This study was to investigate the removal efficiency and kinetics in oxidation of ammonia solutions (NH3-N) in ranging from 400 mg/L to 1000 mg/L by adding Cu/La/Ce catalyst in process of Wet Air Oxidation (denoted by WAO). All experiments were conducted in semi-batch and continuous reactors in series. The major parameters included temperature, pressure, concentration and pH. In the semi-batch type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, temperatures ranging from 423 K to 503 K, a total pressure of 4.0 Mpa, and a pH of 12.0. A removal efficiency of 32.7%was obtained in WAO process at 503 K for180 min, but it could be significantly promote to 95.1% after adding a catalyst of molar ratio 7:2:1.The kinetics of WAO with this catalyst in oxidation of NH3-N solutions, using a test of half-life, was developed nearly to a zero order. The reaction constants were 10.12 KJ/mol, 9.12 KJ/mol, and 6.57 KJ/mol at 503 K, 473 K and 423 K. In the continuous type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, a temperature of 503 K, a total pressure of 2.0 Mpa, a pH of 12.0 and a liquid space velocity of 4.5 hr-1 (averagelyresidence time 14 min) . A removal efficiency of NH3-N of 6.5 % only was achieved in WAO process for a space velocity of 4.5 hr-1 (averagely residence time 14 min) , but after adding a catalyst of molar ratio 7:2:1 it increased to 72.3 % for a same residence time and a better efficiency of above 91 % was found for 1.5 hr-1 (averagely residence time 40 min) . For increasing the initial concentration of NH3-N into 600 mg/L, 800 mg/L, and 1000 mg/L the removal efficiency of NH3-N decreased with 85 %,75 % and 69 % for 1.5 hr-1 . Thus, the initial concentration of NH3-N in influent inhibits the removal efficiency in the oxidation process. The higher initial concentration the lower removal efficiency.

In this work, the steady-state performance of zeolite-based (Cu-ZSM-5) and vanadium-based honeycomb monolith catalysts was investigated in the selective catalytic reduction process (SCR) for NO removal using NH3. The aim was to delineate the effect of various parameters including pretreatment of the catalyst sample with H2, NH3-to-NO ratio, inlet oxygen concentration, and space velocity. The concentrations of the species (e.g. NO, NH3, and others) were determined using a Fourier Transform Infrared (FTIR) spectrometer. The temperature was varied from ambient (25 C) to 500 C. The investigation showed that all of the above parameters (except pre-treatment with H2) significantly affected the peak NO reduction, the temperature at which peak NO reduction occurred, and residual ammonia left at higher temperatures (also known as 'NH3 slip'). Depending upon the particular values of the parameters, a peak NO reduction of around 90% was obtained for both the catalysts. However, an accompanied generation of N2O and NO2 species was observed as well, being much higher for the vanadium-based catalyst than for the Cu-ZSM-5 catalyst. For both catalysts, the peak NO reduction decreased with an increase in space velocity, and did not change significantly with an increase in oxygen concentration. The temperatures at which peak NO reduction and complete NH3 removal occurred increased with an increase in space velocity but decreased with an increase in oxygen concentration. The presence of more ammonia at the inlet (i.e. higher NH3-to-NO ratio) improved the peak NO reduction but simultaneously resulted in an increase in residual ammonia. Pretreatment of the catalyst sample with H2 (performed only for the Cu-ZSM-5 catalyst) did not produce any perceivable difference in any of the results for the conditions of these experiments.

Two flow reactor studies, using an electrically heated laminar flow reactor over Vanadia based (V2O5-WO3/TiO2) honeycomb catalyst, were performed at 1 atm pressure and various temperatures. The experiments were conducted using simulated exhaust gas compositions for different exhaust gases. A quartz tube was used in order to establish inert conditions inside the reactor. The experiments utilized a Fourier transform infrared (FTIR) spectrometer in order to perform both qualitative and quantitative analysis of the reaction products. Urea-water solution decomposition was investigated over V2O5-WO3/TiO2 catalyst over the entire SCR temperature range using the temperature controlled flow reactor. The solution was preheated and then injected into pure nitrogen (N2) stream. The decomposition experiments were conducted with a number of oxygen (O2) compositions (0, 1, 10, and 15%) over the temperature range of 227oC to 477oC. The study showed ammonia (NH3), carbon-dioxide (CO2) and nitric oxide (NO) as the major products of decomposition along with other products such as nitrous oxide (N2O) and nitrogen dioxide (NO2). The selective catalytic reduction (SCR) of nitric oxide (NO) with urea-water solution over V2O5-WO3/TiO2 catalyst using a laboratory laminar-flow reactor was investigated. Urea-water solution was injected at a temperature higher than the vaporization temperature of water and the flow reactor temperature was varied from 127oC to 477oC. A FTIR spectrometer was used to determine the concentrations of the product species. The major products of SCR reduction were NH3, NO and CO2 along with the presence of other minor products NO2 and N2O. NO removal of up to 87% was observed. The aim of the urea-water decomposition experiments was to study the decomposition process as close to the SCR configuration as possible. The aim of the SCR experiments was to delineate the effect of various parameters including reaction temperature and O2 concentration on the reduction process. The SCR investigation showed that changing parameter values significantly affected the NO removal, the residual NH3 concentration, the temperature of the maximum NO reduction, and the temperature of complete NH3 conversion. In the presence of O2, the reaction temperature for maximum NO reduction was 377?C for ratio of 1.0.

Volatile organic compounds (VOCs) can detrimentally affect human health directly and indirectly. However, the main environmental concern of VOCs involves the formation of smog. In the presence of nitrogen oxides, VOCs are the precursors to the formation of ground level ozone. Isopropyl alcohol (IPA) and toluene are extensively used in industry as solvents. They are all highly toxic to animals and humans. Accordingly, IPA and toluene are strongly associated with problems of VOCs. Catalytic incinerations and a regenerative catalytic oxidizer (RCO) were adopted to decompose VOCs herein. Various catalysts were prepared and developed in this study. The screening test of catalytic activity and the influences of the operational parameters on VOCs removal efficiencies were widely discussed through catalytic incinerations of VOCs. The more effective and cheaper catalysts through above discussions of catalytic incineration were selected. And they were utilized in an RCO to investigate their performance in VOCs oxidation and RCO operations. Experimental results demonstrate that 10 wt%CuCo/(G) catalyst performed well in an RCO because it has the excellent performance in incineration efficiency and economic efficiency. The achievements of this study are summarized as follows: (1) Treatment of isopropyl alcohol (IPA) using ceramic honeycomb(CH) catalyst The eighteen ceramic honeycomb catalysts we prepared by various methods (co-precipitation, wet impregnation and incipient impregnation), various metal weight loadings (5 ~ 20 wt %), and various metals (Cu and CuCe) were used in the experiment. The results indicate that 20 wt%CuCe/(CH) catalyst prepared by wet impregnation had the best performance in CO2 yield because TC50 and TC95 were 245¢J and 370¢J, respectively, under the following operating conditions; a space velocity of 12000 hr-1, an inlet IPA concentration of 1600 ppm, an oxygen concentration of 21%, and a relative humidity of 25%. Given the operational parameters of IPA oxidation experiments, the CO2 yields increased with higher temperature and oxygen concentration, but decreased with inlet IPA concentration, space velocity and the relative humidity increased. Moreover, the stability test results show that the 20 wt%CuCe/(CH) catalyst had excellent stability. (2) Treatment of toluene using molecular sieve(MS) catalyst Molecular sieve catalysts with various metals (Cu, Co, Mn, CuMn, CuCo, MnCo) and various loadings (5~10 wt %) were produced by wet impregnation to treat toluene. The results indicate that 10 wt%CuCo/(MS) had the best performance in toluene conversion because T50 and T95 were 295¢J and 425¢J, respectively, at an influent concentration of toluene of 900 ppm, an oxygen concentration of 21%, a space velocity of 12000 hr-1, and a relative humidity of 26%. The conversions of toluene increased with the reaction temperature and the influent concentration of oxygen, but decreased as the initial concentration of toluene and the space velocity increased. Moreover, we did not find any decay between the fresh and used catalysts using SEM and EDS. (3) Treatment of isopropyl alcohol (IPA) using Cu/(CH) and CuCo/(CH) catalysts We used the 20 wt% CuCo/(CH) and 20 wt% Cu/(CH) catalysts in a pilot RCO to test IPA oxidation performance under various conditions. The best catalyst was selected, and the economic efficiency of RCO and the phenomenon of RCO operations were more widely discussed. The results demonstrate that 20 wt% CuCo/(CH) catalyst performed well in an RCO because it was effective in treating IPA, with a CO2 yield of up to 95%. It also had the largest tolerance of variations in inlet IPA concentration and gas velocity. The 20 wt% CuCo/(CH) catalyst in an RCO also performed well in terms of TRE, pressure drop and selectivity to CO2. The thermal recovery efficiency (TRE) decreased as gas velocity increased. The temperature difference (Td) and pressure drop increased with gas velocity and heating zone temperature. The TRE range was from 87.8 to 91.2 % and the Td ranged from 22.1~35.1¢Junder various conditions. Finally, the stability test results indicate that the 20 wt% CuCo/(CH) catalyst was very stable at various CO2 yields and temperatures. (4) Treatment of toluene using CuCo/(CH) catalysts with various carriers In this work, three catalysts (10 wt%CuCo/(G)¡B10 wt%CuCo/(MS) and 20 wt% Cu/(CH)) were prepared by wet impregnation, and used in an RCO to test their performance in incineration efficiency and economic efficiency under various operational conditions. Then the best catalyst was selected and the phenomenons of RCO operations were further investigated. Experimental results demonstrate that 10 wt%CuCo/(G) catalyst performed well in an RCO because it is effective in treating toluene with a toluene conversion of up to 95% at the heating zone temperature (Tset) = 400¢J under various conditions. The 10 wt% CuCo/(G) catalyst had the greatest tolerance against the effects of inlet toluene concentration and gas velocity, and exhibited the best performance in terms of TRE , Td and pressure drop. The TRE range was from 90.2 to 92.9 % and Td ranged from 18.2 to 30.9¢J under various conditions at Tset = 300~400¢J. Moreover, when 10 wt% CuCo/(G) catalyst was used in an RCO, the results demonstrate that (1) high selectivity to CO2 ; (2) decrease in TRE and increase in Td as increasing the shifting time; (3) an insignificant effect of shifting time on pressure drop and (4) excellent stability of 10 wt% CuCo/(G) catalyst in a long period test.

In industrial wastewater, there are usually many kinds of organics and heavy metals and can cause damage on human health and environment without well treatment. Printed Circuit Board (PCB) industrial wastewater is a typical example due to the complicated manufacture processes and the use of specific chemicals. In this study, the PCB industrial wastewater is collected and then treated by the combination of Fenton method and Ferrite Process (or called Fenton-Ferrite Process, FFP). Moreover, the recycling possibility of sludge generated from FFP is also studied. Through this study, the treatment procedure of wastewater containing organics heavy metals is established and the direction of sludge reuse is also provided. To realize the characteristic of PCB industrial wastewater, the wastewater from some PCB factory in southern Taiwan was firstly collected and analyzed to identify the pollution concentrations and then treated by FFP. The experimental results showed that the optimum parameters of Fenton method in FFP were pH = 2, [Fe2+]= 500 mg/L, [H2O2]= 3000 mg/L, reaction time= 60 min and batch dosing, and the residual COD and TOC were 84.9 mg/L and 58.3 mg/L under the COD regulation standard 120 mg/L. Meanwhile, the proper conditions of Ferrite Process in FFP were pH= 10, reaction temperature= 80¢J, reaction time= 40 min, aeration rate= 3 L/min/L wastewater, Fe/Cu molar ratio= 10 and three-stage reaction. Under that circumstance, the residual [Cu2+] in wastewater was 0.18 mg/L and the Toxicity Characteristic Leaching Procedure (TCLP) test of sludge from FFP was 4.58 far below the effluent standard 3 mg/L and TCLP standard 15 mg/L. The properties of sludge were further investigated by X-Ray Diffractometer (XRD), Scanning Electron Microscope (SEM) and Superconducting Quantum Interference Device (SQUID). The pattern of XRD indicated that the major structures were Fe3O4 and CuFe2O4; the figure of SEM showed that the surface of sludge was composed of many round particles and the distribution of particle size was from 50 nm-100 nm; the magnetic property analyzed by SQUID showed that the saturation moment was 62.85 emu/g. In the research of sludge applied in catalytic incineration, the o-xylene conversion was 97 % by sludge but only 31 % by quartz sand at 400 ¢J. Moreover, in the 72 hr-decay test of catalyst, the results clearly indicated that the performance did not obviously decline and there were no any byproducts but CO2. Therefore, the investigation revealed that the sludge had great potential in catalytic reaction. The catalytic performance of various ferrospinels generated from different manufactured conditions was also studied. Through the screening of catalysts, the order of various ferrospinels activity was Cu-ferrite > Mn-ferrite > ferrite ¡Ü Zn-ferrite and the most effective Cu-ferrite was manufactured at pH= 9 and T= 90 ¢J. After 72 hr test, the decay of catalyst was not also found. In the examination of Cu-ferrite physical property, the XRD pattern showed that the structure was CuFe2O4; the figure of SEM illustrated that there was no difference between the surface of fresh and used catalyst; the magnetic property measured by SQUID showed that the saturation moment was 30.89 emu/g.

Oil storage tanks and their pipelines are mostly constructed under the ground. If the leaches are occurred, the soil pollution and the contamination of groundwater quality will influenced seriously. The soil of oil polluted sites is usually containing the huge amounts of volatile organic compounds (VOCs) and other organics. These VOCs is uncomfortable on physical body when they spread into atmosphere not only to cause the harm of human health but also to react into photochemical smog. Besides, the VOCs are probably reacting with nitrogen oxides into the problems of high concentrations of ozone. In this study, we used a regenerative catalytic oxidizer (RCO) to deal with VOCs in soil of the oil polluted sites. The RCO system was packed with self-made catalyst of 20 wt%CuMn/£^-Al2O3. Experimental results revealed 90¡Ó5% of the influent VOCs (C0=450-10,000 ppm) was thermally destruction with no catalyst in beds operated with a valve shifting time (ts) of 2 min, superficial gas velocities (Ug) of 0.37 m/s (evaluated at an influent air temperature of around 30¢J) and present maximum destruction temperature (TS) of 800-900¢J. With the catalyst packings and operation conditions of Ug=0.37 m/s and C0=450~10,000 ppm, the destruction efficiency of 93.35 and 96.5% were observed, respectively in average at TS of 600 and 650¢J. When Ug=1.11 m/s and C0=450-10,000 ppm, the destruction efficiency of 87.51 and 93.75% were observed, respectively in average at TS of 600 and 650¢J. The destruction efficiency of RCO is high at higher influent concentration of VOCs and low gas velocities at TS=600-650¢J.

The fractional catalytic pyrolysis of pine was studied both experimentally and through models. A preliminary stage economic analysis was conducted for a wood chip pyrolysis facility operating at a feed rate of 2000 wet ton/day for producing bio-oil. In the experimental study, multiple grams of bio oil were produced in a single run to facilitate the more extensive characterization of the oil produced from pyrolysis of biomass impregnated with different catalysts. Two reactors configurations, a screw extruder and a tubular pyrolysis reactor, were explored to perform fractional catalytic pyrolysis of biomass. The main aim of performing a wood pyrolysis reaction in a modified screw extruder is to facilitate the simultaneous collection of bio-oil produced from staged temperature pyrolysis of three main components of wood, cellulose, hemicellulose and lignin, at a reasonable scale. Apart from complete characterization of bio-oil, this will enable us to study the effect of various selected catalysts on the quality of bio-oil and the percentage of char produced, and the influence of process parameters on chemical composition of the pyrolysis oils. These experiments were later performed in a tubular pyrolysis reactor due to the difficulty of making different parts of the extruder work well together. The goal of these experiments is to produce bio-oil in multiple grams from fractional catalytic pyrolysis of wood. This will enable us to study the effect of catalyst on the chemical composition of the oil and percentage of char produced. In the modeling studies, a model of an auger reactor comprised of three different zones run at different temperatures to facilitate the collection of oil from pyrolysis of three major components of wood, namely cellulose, hemicelluloses and lignin, was developed. The effect of residence time distribution (RTD), and zone temperatures based on kinetic models on the yield of products was studied. Sensitivity of the Arrhenius rate constants calculated from synthetic data with respect to small variations in process parameters was evaluated. In the economic analysis of a wood chip pyrolysis facility, mass and energy calculations were performed based on a feed rate of 2000 wet tons/day of wood chips to the dryer. The cost of bio-oil at 10% return on investment was proposed and the sensitivity of the selling price of bio-oil with respect to capital and operating costs was analyzed. The experimental study will serve as a benchmark in exploring the above mentioned reactor configurations further. Alkali metal carbonates were used to study the quality of oil produced from pine pyrolysis. It was established that these catalysts, when added in the same molar ratio basis, increase the percentage of char. However, complete characterization of these oils for different catalysts needs to be done. Systems modeling of pyrolysis in an auger reactor established that the kinetic parameters (depending on experimental set up) and the RTD (Residence Time Distribution) parameters play a crucial role in determining the yield of oil. Variations in temperature of zone 3 play a crucial role in varying the output of oil whereas variations in temperatures of zones 2 and 1 do not significantly impact the output of oil. For a given reaction kinetic scheme for the pyrolysis reactions, calculated values of the kinetic rate constants are not sensitive to errors in experimental conditions. It was also established that the experimental error in calculation of the RTD parameters can induce error in calculation of the Arrhenius constants but these values can still predict the yield of products accurately. In the economic analysis of wood chip pyrolysis, the selling price of the bio-oil according to the cost calculation is projected to be $1.49/gal. The production cost of bio-oil is $ 1.20/gal. The cost of bio-oil is extremely sensitive to variations in operating cost (for example, cost of feed stock and selling price of char) and is not significantly affected by the variations in capital cost.

<p>Due to continuously stricter regulations regarding emissions from power generation processes, development of existing gas turbine combustors is essential. A promising alternative to conventional flame combustion in gas turbines is catalytic combustion, which can result in ultra low emission levels of NO_x, CO and unburned hydrocarbons. The work presented in this thesis concerns the development of methane oxidation catalysts for gas turbine combustors. The application of catalytic combustion to different combustor concepts is addressed in particular.</p><p>The first part of the thesis (Paper I) reports on catalyst development for fuel-lean methane combustion. The effect on catalytic activity of diluting the reaction mixture with water and carbon dioxide was studied in order to simulate a combustion process with exhaust gas recirculation. Palladium-based catalysts were found to exhibit the highest activity for methane oxidation under fuel-lean conditions. However, the catalytic activity was significantly decreased by adding water and CO₂, resulting in unacceptably high ignition temperatures of the fuel.</p><p>In the second part of this thesis (Paper II), the development of rhodium catalysts for fuel-rich methane combustion is addressed. The effect of water addition on the methane conversion and the product gas composition was studied. A significant influence of the support material and Rh loading on the catalytic behavior was found. The addition of water influenced both the low-temperature activity and the product gas composition.</p>

No description available.

<p>Catalytic combustion is an environmentally friendlytechnique to combust fuels in e.g. gas turbines. Introducing acatalyst into the combustion chamber of a gas turbine allowscombustion outside the normal flammability limits. Hence, theadiabatic flame temperature may be lowered below the thresholdtemperature for thermal NO_Xformation while maintaining a stable combustion.However, several challenges are connected to the application ofcatalytic combustion in gas turbines. The first part of thisthesis reviews the use of catalytic combustion in gas turbines.The influence of the fuel has been studied and compared overdifferent catalyst materials.</p><p>The material section is divided into two parts. The firstconcerns bimetallic palladium catalysts. These catalysts showeda more stable activity compared to their pure palladiumcounterparts for methane combustion. This was verified both byusing an annular reactor at ambient pressure and a pilot-scalereactor at elevated pressures and flows closely resembling theones found in a gas turbine combustor.</p><p>The second part concerns high-temperature materials, whichmay be used either as active or washcoat materials. A novelgroup of materials for catalysis, i.e. garnets, has beensynthesised and tested in combustion of methane, a low-heatingvalue gas and diesel fuel. The garnets showed some interestingabilities especially for combustion of low-heating value, LHV,gas. Two other materials were also studied, i.e. spinels andhexaaluminates, both showed very promising thermal stabilityand the substituted hexaaluminates also showed a good catalyticactivity.</p><p>Finally, deactivation of the catalyst materials was studied.In this part the sulphur poisoning of palladium, platinum andthe above-mentioned complex metal oxides has been studied forcombustion of a LHV gas. Platinum and surprisingly the garnetwere least deactivated. Palladium was severely affected formethane combustion while the other washcoat materials were mostaffected for carbon monoxide and hydrogen.</p><p><b>Keywords:</b>catalytic combustion, catalyst materials,palladium, platinum, bimetallic, garnet, spinel, hexaaluminate,deactivation, sulphur, poisoning, diesel, methane,hydrocarbons</p>