RESUMO
A detailed techno-economic comparison of a chemical scrubber (CS) and a bio-filter (BF) was conducted over a 45-day time period at a municipal wastewater treatment plant (WWTP), Yazd city. The assessment of emissions quantity indicated that odor emissions from the Yazd WWPT mainly consist of hydrogen sulfide (H2S) and ammonia (NH3). It was also found that odor gaseous loading changes corresponding to water consumption pattern in society (R2â¯=â¯0.922) for H2S and (R2â¯=â¯0.978) for NH3. The highest level of 25 and 3â¯ppm for H2S and NH3, respectively were detected at specific times during the day. The BF system was continuously supplied with Yazd WWPT's off-gas treatment while the CS was only examined at the times during the day when the gas emissions are at the highest level. The removal efficiency of NH3 and H2S were found to be affected by their respective loading rate. Additionally, among the various oxidants examined in the CS, the NaOCl solution showed the best results in terms of removal efficiency and compatibility. The experiment revealed almost complete removal of NH3 while the H2S removal efficiency remained above 95% for both systems regardless of the operating conditions. This study clearly demonstrates the effectiveness of both systems in treating actual waste gases containing H2S and NH3. By comparing the gas loading rate of both systems and considering limitations of the BF system, the CS seems to be more efficient applicable odor control technology from a technical viewpoint. From the economic viewpoint, comparisons revealed that chemical usage and operating expenses were costly parts of the CS and the BF, respectively. The economic indexes of 1.58 .m-3. h-1 and 2.57 .m-3. h-1 were obtained for the BF and CS, respectively, reflecting cost-effectiveness of the BF system.
Assuntos
Poluentes Atmosféricos , Sulfeto de Hidrogênio , Amônia , Análise Custo-Benefício , Filtração , Águas ResiduáriasRESUMO
This study aims to provide a comprehensive evaluation of the photocatalytic properties and performance of the Cu-Ti-O heterojunction sonochemically embedded in the mesoporous silica matrix. Various characterization analyses and adsorption/photodegradation experiments were performed to assess the potential of the sample for tetracycline (TC) removal. The characterization results indicated that sonication contributes to better dispersion of Ti-Cu-O species, resulting in more uniform particle sizes, stronger semiconductors-silica interaction, and less agglomeration. Furthermore, sonication significantly affected the optical nanocomposite features, leading to an improvement in charge carrier separation and a decrease in the band gap of Ti-Cu-Si (S) by approximately 2.6 eV. Based on the textural results, the ultrasound microjets increased the surface area and pore volume, which facilitate mass transfer and provide suitable adsorption sites for TC molecules. Accordingly, Cu-Ti-Si (S) demonstrated higher adsorption capacity (0.051 g TC/g adsorbent) and eliminated TC significantly faster (0.0054 L.mg-1.min-1) than a non-sonicated sample during 120 min of irradiation, resulting in 2.84 times improvement in the constant rate. In addition, experimental results were accurately modeled using a central composite design in combination with response surface methodology (RSM) and artificial neural networks (ANN) to predict and optimize TC photodegradation. Both RSM and ANN models revealed excellent predictability for TC degradation efficiency, with R2 = 99.47 and 99.71%, respectively. At optimal operational conditions (CTC = 20 ppm, photocatalyst dosage = 1.15 g.L-1, pH = 9, and irradiation time = 100 min), more than 95% and 87% of TC were degraded within the UV (375 W) and simulated solar light (400 W) irradiation periods, respectively. It was observed that the Cu-Ti-Si (S) nanocomposite maintained remarkable stability after four cycles with only a negligible 3% loss of activity, owing to the superior interaction between the bimetallic heterojunction and the silica matrix.
Assuntos
Dióxido de Silício , Titânio , Fotólise , Dióxido de Silício/química , Adsorção , Titânio/química , Tetraciclina/química , Antibacterianos , Redes Neurais de ComputaçãoRESUMO
Photodegradation of paraquat herbicide was assessed over several TiO2-WO3 heterojunctions embedded in the diatomite matrix. The characterization results indicated that WO3 embedding in the TiO2 decorated-diatomite matrix could not only enhance the adsorption capacity, visible-light response, and distribution of semiconductor species but also lessen the recombination rate and band gap energy. These characteristics were more noticeable as 5 wt.% of WO3 was embedded. Despite better optical properties of immobilized TiO2-WO3 nanocomposites, overloading WO3 generally alleviates the synergetic effect of tungsten due to surface coverage of diatomite matrix and, subsequently, the significant attenuation of textural properties, more formation of agglomerations and defects as trapping centers in the oxidation sites of heterostructures, and also, less likely of forming TiO2-WO3 heterojunction. In accordance with characterization results, the highest UV-photodegradation of paraquat was attained over heterostructured nanocomposite containing 5 wt.% WO3 (T25-W5/Di). The effects of significant operating parameters were also investigated, modeled, and optimized using response surface methodology (RSM)-central composite design (CCD). Under optimized operation conditions, the experimental removal efficiency of paraquat reached 97.1 and 80% using UV and simulated solar light, respectively. Moreover, the reusability results confirm the sustained activity of the T25-W5/Di nanocomposite.
Assuntos
Herbicidas , Paraquat , FotóliseRESUMO
In this research, tetracycline photodegradation under UV light was investigated over bare TiO2 and a series of MCM-41 supported CuO-TiO2 heterojunctions varying in CuO content with the intent of exploring the effect of MCM-41 presence and especially, CuO addition. Several techniques including XRD, FESEM, EDX, DRS, BET, and PL were applied to characterize the physicochemical and photophysical properties of synthesized nanocomposites. It was found that the co-existence of MCM-41 and CuO enhances the surface dispersion of Ti species, leading to less number of agglomerates and smaller particle size of TiO2, which it promoted photophysical properties and reinforced the interaction of surface species with the support and thereby, the photosite leachings were lessened. However, the excessive loadings alleviate the synergetic effect of CuO due to the significant decrease of surface area, the appearance of more number of agglomerations, and surface coverage of MCM-41. The results revealed that CuO addition not only enhances the photocatalytic activity of TiO2/MCM-41 but also makes it reusable in further experiments. It was also observed that the highest photodegradation of tetracycline was obtained over TiO2-CuO/MCM-41 nanocomposite containing 5 wt% CuO. It is attributed to less electron-hole recombination, appropriate band gap, smaller number of agglomerations, and more uniform dispersion of photosites. Following the obtained results, a possible reaction mechanism was also proposed.
Assuntos
Nanopartículas , Antibacterianos , Catálise , Cobre , Fotólise , Dióxido de Silício , Titânio , Difração de Raios XRESUMO
The catalytic performance of nanostructured Ni-Co/Al2O3-ZrO2 catalysts, prepared by ultrasound-assisted impregnation method was examined in the dry reforming of methane. The effect of irradiation power and irradiation time have been studied by changing time (0, 20, 80min) and power of the sonication (30, 60, 90W) during the synthesis which resulted in different physiochemical properties of the nanocatalyst. The nanocatalysts were characterized by XRD, FESEM, PSD, EDX, TEM, TPR-H2, BET, FTIR and TG analyses. Based on the characterization results, ultrasound treatment endowed the sample with more uniform and smaller nanoparticles; higher surface area, stronger metal-support interaction and more homogenous dispersion. Moreover, the analyses exhibited smaller particles with higher surface area and less population of particle aggregates at longer and highly irradiated nanocatalysts. The nanocatalyst irradiated at 90W for 80min (the longest irradiation time and the most intense power) showed a uniform morphology and a very narrow particles size distribution. More than 65% of particles of this nanocatalyst were in the range of 10-30nm. Activity tests demonstrated that employing ultrasound irradiation during impregnation improves feed conversion and products yield, reaching values close to equilibrium. Among sonicated nanocatalysts, with increasing power and time of irradiation, the nanocatalyst represents higher activity. The superior performance amongst the various bimetallic catalysts tested was observed over the catalyst with 90W and 80min ultrasonic irradiation which is stable in 24h time on stream test. The excellent anti-coking performance of this bimetallic catalyst, confirmed by TG and FESEM analyses of spent catalyst, is closely related to the promoting effect of sonication on the metal-support interaction, Ni dispersion and particle size; and probably, the synergy between metallic species.
RESUMO
CO2-enhanced oxidative dehydrogenation of ethane was investigated over sonochemically synthesized Cr/clinoptilolite-ZrO2 nanocatalyst with the aim of assessing the effect of composite support and ultrasonic irradiation on the nanocatalyst reactivity and stability. To this aim, ZrO2 promoted clinoptilolite supports varying in zirconia content (0, 25, 50wt%) were synthesized by hydrothermally precipitation method and impregnated with chromium nitrate under ultrasound irradiation. The samples were characterized by XRD, FESEM, EDX, TEM, ICP, BET, FTIR, TPR-H2 and TPD-NH3 techniques. The characterization results indicated that ultrasound irradiation could not only reduce the formation of Cr2O3 and decrease submicron particle size of chromium oxide to nanometer scale, but also promote the distribution of metallic particles and strengthen the chromium-support interaction. As a result, utilizing ultrasound irradiation in the synthesis of Cr/Clinoptilolite helped to maintain a high and stable catalytic activity. These features were more prominent in the presence of zirconia. It was found that the metal oxide nanoparticles with about 4-8nm are dispersed uniformly on the surface of composite support containing 25wt% ZrO2 (CLT-Z25). Moreover, the addition of ZrO2 resulted in the formation of new strong acid sites and a significant modification in the reducibility of chromium species, which alongside homogenous and small Cr nanoparticles account for the superior catalytic performance of ZrO2 containing samples. However, excessive loading of ZrO2 (50wt%) severely covered the surface of clinoptilolite, afforded the aggregations of metallic particles and thereupon, weakened the contact between clinoptilolite and ZrO2, which together with more acid strength seriously resulted in the deactivation of catalyst. In spite of superior initial activity of ZrO2-rich sample among the catalysts tested, ultrasonic synthesized Cr/CLT-Z25 nanocatalyst showed the best catalytic performance after 5h-catalytic reaction.
RESUMO
The bimetallic Pd-Cu nanocatalysts with different Pd loadings and ultrasonic irradiation times were sonochemically synthesized and their activities toward CO oxidation were investigated. XRD, FESEM, TEM, BET, FTIR and TG-DTG techniques were employed in nanocatalysts characterization. XRD data confirmed formation of CuAl2O4 spinel with an average crystallite size of 4.9 nm. FESEM images revealed more uniform pattern and also fewer agglomerations were observed by increasing ultrasonic irradiation time. In agreement with FESEM result, TEM images depicted nanoparticles and uniform dispersion of active phase over alumina. BET surface analysis showed that increasing the Pd loading has no significant effect on surface area; whereas by increasing irradiation time the surface area increases slightly. Catalytic performance tests of synthesized samples showed that Pd(1.5%)-Cu(20%)/Al2O3 with 95 min ultrasonic irradiation time had the best activity over the course of reaction. In addition, increasing CO at feed composition revealed that among synthesized nanocatalysts with 0.5%, 1% and 1.5% of Pd, synthesized sample with 1.5% of Pd had the best low-temperature activity.