Hot-melted asphalt (HMA) plants use sized gravels, asphalt and/or recycled asphalt as raw materials. In the plant, the materials are heated to certain preset temperatures and blended at fixed ratios at around 170oC to prepare the required HMA for road paving. In the asphalt-melting, hot-blending and dumping operations, fumes and particulates emit from the process equipments. The emitted gases contain various volatile organic compounds (VOCs) and poly aromatic hydrocarbons (PAHs) which are harmful to the health of the plant workers and nearby residents. Complaints from the residents also come with the fume and odorous emissions. In this study, an oxidation-reduction-in-series scrubbing process was tested to remove odorous compounds in waste gases emitted from HMA plants. Waste gas samples for test were collected from the vent hole of an oven which contains a heated sample of asphalt or recycled asphalt concrete. Sodium hypochlorite solution was used to scrub and oxidize the compounds and hydrogen peroxide to reduce the chlorine emitted from the oxidative scrubber. A gas chromatography with a mass spectrophotometric detector (GC-MSD) was used for the identification of the odorous species and their concentrations in the waste gases. Sensory tests were also used to determine the odor removal efficiency. GC-MSD examination results indicates that alkanes, arenes, alkenes, halides, esters, and carbonyl compounds were detected in the test gas. Scrubbing test results indicate that with oxidative solution of 50-60 mg/L residual chlorine at pH 7.0-7.5 and reductive solution of 35 mg/L hydrogen peroxide at pH >12, over 90% of the VOCs in the tested gas could be removed. Odor intensities could be reduced from 3,090 (expressed as dilutions to threshold) to 73. Pungent asphalt odor in the test gas was turned into slight sulfur smell after the scrubbing. For removing the odors from 500 Nm3/min of the flue gas vented from a HMA plant, an analysis indicates the required total cost for chemicals (sodium hypochlorite solution, hydrogen peroxide and sodium hydroxide) added to the scrubbers was around 2,800 NT$/day (US$ 95/day) for a daily operation time of 10 hours. The cost is far lower than that by the traditional thermal incineration one (25,000 NT$/day or US$ 850/day) or by the regenerative thermal oxidation (RTO) one (14,300 NT$/day or US$ 485/day). This study has successfully developed an economical and effective chemical scrubbing technology for the removal of odorous compounds in gases emitted from HMA plants.

This study was aimed at the removal of odorous compounds in gases emitted from rubber processing industries. Odorous gas for test was prepared by mixing fresh air and an odorous gas drawn from an oven in which a sample of rubber powder was kept at 160 and 200 oC, respectively. For ozonation tests, the prepared odorous gas was then premixed with a definite amount of ozone-enriched air before entering into a contact system. The contact system consists of two sieve-plate columns connected in series and each column has four 1-L chambers. Depending on with or without introducing a circulating scrubbing water into the columns, the oxidation reaction could be either wet or dry one. For UV/ozonation (UV/O3) tests, batch reactions were performed in a 3.63-L chamber fitted with an UV lamp inserted in a quartz column. A definite volume of the odorous gas generated from the oven was injected into the chamber containing a definite concentration of ozone. Results from the dry-ozonation tests indicate that that 82 and 70% of VOCs and odorous intensity in the influent gas could be removed, respectively, with the operation conditions of an initial ozone concentration of 4.0 ppm, VOC (methane equivalent) concentrations of 6.5-9.0 ppm, an oxidation temperature of 38.5 oC, and a gas empty-bed-retention time (EBRT) of 8.6 s. Both the VOC and odorous intensity removal efficiencies were roughly proportional to the EBRT in the range of 1.4-11.4 s. Wet-ozonation got 97 and over 90% of VOC and odorous intensity removal, respectively, with the operation conditions of initial ozone concentration 4.0 ppm, VOC (methane equivalent) concentrations 6.5-10.3 ppm, oxidation temperature 37.3 oC, gas EBRT 12 s, and liquid/gas rate ratio 0.01 m3/m3. With conditions similar to those cited above, odor concentration (dilutions to the threshold) in the test gas could be removed from 3,090 to 130 with an EBRT of 14.5 s. Tests also indicate that activated carbon is effective for both physical and chemical removals of the residual VOCs, odorous compounds, and ozone in the effluent gas from the ozonation system. Economical analysis indicates that around NT$ 5.4 is required for treating 1,000 m3 of the tested foul gas by the proposed wet-ozonation and activated carbon adsorption process. Odor concentration (dilutions to the threshold) in a test could be reduced from around 4,000 to 70. Results of UV/O3 tests indicate that the introduction of the 185 nm UV irradiation at the intensity of 5W/3.63L did not help in the additional VOC and odor removals with an initial ozone concentration 4.0 ppm, VOC (methane equivalent) concentrations of 12.2-15.0 ppm, oxidation temperature of 31.5 oC, and reaction time 18.2 s. UV irradiation is not necessary for the ozonation odor removal of the test gas samples.

This thesis focuses on the synthesis and applications of nanoscale zero valent iron (nZVI) in the environmental remediation of contaminants. The polyvalent characteristics of this nanomaterial are evaluated in this work with the study of its application in a wide range of contaminants: heavy metals and pesticides in water medium, and malodorous sulfur compounds present in air streams. Moreover, a novel method of synthesis of encapsulated nZVI from a waste material is presented, which meets the principles of green chemistry and at the same time represents a low-cost method of obtaining nZVI with improved characteristics. Chapter 1 describes the current state of the topics that will be discussed in the rest of the thesis. Specifically, the different mechanisms of contaminant remediation by nZVI are discussed, a summary of the current synthesis methods is presented and the principal modifications of nZVI to improve its characteristics are described. Finally, the limitations of the current techniques are assessed, which will be the starting point of the thesis. In Chapter 2, the application of nZVI to heavy metal removal during long time periods is explored. The contaminants studied are Zn, Cd, Ni, Cu and Cr, which are the most common heavy metals found in ground and wastewater. A delivery-effect of the heavy metal ions that had already been attached to nZVI surface is observed after long reaction times, which is a consequence of the nZVI aging and oxidation. The conditions that influence the delivery-effect are assessed and possible solutions to this detected problem are presented. In Chapter 3, nZVI is applied to the removal of sulfur-based odorous compounds in air streams. The compounds studied are hydrogen sulfide and dimethyl disulfide (DMDS), which are commonly found in wastewater treatment plants. Both nZVI loading and pH are varied to assess their influence on the process. Bimetallic nanoscale particles of Cu/Fe, Ni/Fe and Pd/Fe are synthesized in order to improve the DMDS abatement by the nZVI. The advantages of this new method for odor removal are discussed at the look of the experimental results. Lastly, a pilot scale test was performed in a wastewater treatment plant in order to test the effectiveness of the nZVI in a real application. The nZVI were applied in a scrubber to eliminate the sulfurous compounds from the pre-treatment area of the wastewater treatment plant. Chapter 4 deals with the application of nZVI to the oxidation of non-biodegradable pollutants by the Fenton reaction. Specifically, the effect of pH on the degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) is studied. The advantages of using nZVI as a Fenton reagent compared to homogeneous Fenton are described. Furthermore, the addition of UV-light to the process is investigated. Finally, the main degradation intermediates of the reaction are identified and a degradation mechanism is accordingly proposed. In Chapter 5, the presence of polychlorinated dioxins and furans (PCDD/Fs) in the nZVI surface is addressed. Studies have shown that nZVI enhances the formation of such chlorinated compounds during thermal processes, but it is unclear which the origin of the compounds is. It has been suggested that nZVI could possess impurities such as PCDD/Fs in its surface. Therefore, the concentration of PCDD/Fs in both commercial and laboratory-synthesized nanoparticles is analyzed. PCDD/Fs pattern and WHO-TEQ concentrations are also obtained. As an outcome of the results obtained in this chapter, a recommendation for preventing the PCDD/Fs presence in nZVI is given. Chapter 6 is dedicated to the synthesis of carbon-encapsulated nanoparticles using hydrothermal carbonization (HTC) of an agricultural waste, particularly, olive mill wastewater (OMW). This novel method, in addition to meet the green chemistry principles, makes profit of the high polyphenol content of OMW to maximize the fraction of incorporated iron into the nZVI. Moreover, the carbon layer surrounding the nZVI protects it against oxidation and avoids its aggregation. Several HTC conditions are explored to study their implications in the characteristics of the material obtained. A deep characterization of the encapsulated nZVI is also presented in this chapter. In Chapter 7, the applications of the encapsulated nZVI synthesized in Chapter 6 are explored and compared for the same contaminants that have been studied in the previous chapters. Then, the advantages of encapsulated nZVI in comparison with common nZVI are discussed at the end of the chapter, and an estimation of the synthesis costs with this method is addressed. Lastly, in Chapter 8, the main conclusions of the thesis are summarized and suggestions for future work are presented.