High performance sorbents for flue gas desulfurization can be synthesized by hydration of coal fly ash, calcium sulfate, and calcium oxide. In general, higher desulfurization activity correlates with higher sorbent surface area. Consequently, a major aim in sorbent synthesis is to maximize the sorbent surface area by optimizing the hydration conditions. This work presents an integrated modeling and optimization approach to sorbent synthesis based on statistical experimental design and two artificial intelligence techniques: neural network and genetic algorithm. In the first step of the approach, the main and interactive effects of three hydration variables on sorbent surface area were evaluated using a full factorial design. The hydration variables of interest to this study were hydration time, amount of coal fly ash, and amount of calcium sulfate and the levels investigated were 4-32 h, 5-15 g, and 0-12 g, respectively. In the second step, a neural network was used to model the relationship between the three hydration variables and the sorbent surface area. A genetic algorithm was used in the last step to optimize the input space of the resulting neural network model. According to this integrated modeling and optimization approach, an optimum sorbent surface area of 62.2m(2)g(-1) could be obtained by mixing 13.1g of coal fly ash and 5.5 g of calcium sulfate in a hydration process containing 100ml of water and 5 g of calcium oxide for a fixed hydration time of 10 h.
Siliceous materials such as rice husk ash (RHA) have potential to be utilized as high performance sorbents for the flue gas desulfurization process in small-scale industrial boilers. This study presents findings on identifying the key factorfor high desulfurization activity in sorbents prepared from RHA. Initially, a systematic approach using central composite rotatable design was used to develop a mathematical model that correlates the sorbent preparation variables to the desulfurization activity of the sorbent. The sorbent preparation variables studied are hydration period, x1 (6-16 h), amount of RHA, x2 (5-15 g), amount of CaO, x3 (2-6 g), amount of water, x4 (90-110 mL), and hydration temperature, x5 (150-250 degrees C). The mathematical model developed was subjected to statistical tests and the model is adequate for predicting the SO2 desulfurization activity of the sorbent within the range of the sorbent preparation variables studied. Based on the model, the amount of RHA, amount of CaO, and hydration period used in the preparation step significantly influenced the desulfurization activity of the sorbent. The ratio of RHA and CaO used in the preparation mixture was also a significant factor that influenced the desulfurization activity of the sorbent. A RHA to CaO ratio of 2.5 leads to the formation of specific reactive species in the sorbent that are believed to be the key factor responsible for high desulfurization activity in the sorbent. Other physical properties of the sorbent such as pore size distribution and surface morphology were found to have insignificant influence on the desulfurization activity of the sorbent.
In this work, the removal of SO(2) and NO from simulated flue gas from combustion process was investigated in a fixed-bed reactor using rice husk ash (RHA)/CaO-based sorbent. Various metal precursors were used in order to select the best metal impregnated over RHA/CaO sorbents. The results showed that RHA/CaO sorbents impregnated with CeO(2) had the highest sorption capacity among other impregnated metal oxides for the simultaneous removal of SO(2) and NO. Infrared spectroscopic results indicated the formation of both sulfate (SO(4)(2-)) and nitrate (NO(3)(-)) species due to the catalytic role played by CeO(2). Apart from that, the catalytic activity of the RHA/CaO/CeO(2) sorbent was found to be closely related to its physical properties (specific surface area, total pore volume and average pore diameter).
A recent rise in crab aquaculture activities has intensified the generation of waste shells. In the present study, the waste shells were utilized as a source of calcium oxide to transesterify palm olein into methyl esters (biodiesel). Characterization results revealed that the main component of the shell is calcium carbonate which transformed into calcium oxide when activated above 700 degrees C for 2 h. Parametric studies have been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 5 wt.%; reaction temperature, 65 degrees C; and a stirring rate of 500 rpm. The waste catalyst performs equally well as laboratory CaO, thus creating another low-cost catalyst source for producing biodiesel. Reusability results confirmed that the prepared catalyst is able to be reemployed up to 11 times. Statistical analysis has been performed using a Central Composite Design to evaluate the contribution and performance of the parameters on biodiesel purity.
Aquaculture activity has increased the population of crab, hence increasing the generation of related wastes, particularly the shell. In addition, the number of molting process in crabs compounds further the amount of waste shell generated. As such, in the present work, the application of the waste crab shell as a source of CaO in transesterification of palm olein to biodiesel (methyl ester) was investigated. Preliminary XRD results revealed that thermally activated crab shell contains mainly CaO. Parametric study has been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 4 wt. %; and reaction temperature, 338 K. As compared to laboratory CaO, the catalyst from waste crab shell performs well, thus creating another low-cost catalyst source for producing biodiesel as well as adding value to the waste crab shell. Reusability of crab shell CaO has also been studied and the outcome confirmed that the catalyst is capable to be reutilized up to 11 times, without any major deterioration.
In this work, the application of response surface and neural network models in predicting and optimizing the preparation variables of RHA/CaO/CeO(2) sorbent towards SO(2)/NO sorption capacity was investigated. The sorbents were prepared according to central composite design (CCD) with four independent variables (i.e. hydration period, RHA/CaO ratio, CeO(2) loading and the use of RHA(raw) or pretreated RHA(600 degrees C) as the starting material). Among all the variables studied, the amount of CeO(2) loading had the largest effect. The response surface models developed from CCD was effective in providing a highly accurate prediction for SO(2) and NO sorption capacities within the range of the sorbent preparation variables studied. The prediction of CCD experiment was verified by neural network models which gave almost similar results to those determined by response surface models. The response surface models together with neural network models were then successfully used to locate and validate the optimum hydration process variables for maximizing the SO(2)/NO sorption capacities. Through this optimization process, it was found that maximum SO(2) and NO sorption capacities of 44.34 and 3.51 mg/g, respectively could be obtained by using RHA/CaO/CeO(2) sorbents prepared from RHA(raw) with hydration period of 12h, RHA/CaO ratio of 2.33 and CeO(2) loading of 8.95%.
In this study, methyl ester (ME) was produced by transesterification of palm oil (CPO) (cooking grade) using activated carbon supported calcium oxide as a solid base catalyst (CaO/AC). Response surface methodology (RSM) based on central composite design (CCD) was used to optimize the effect of reaction time, molar ratio of methanol to oil, reaction temperature and catalyst amount on the transesterification process. The optimum condition for CPO transesterification to methyl ester was obtained at 5.5 wt.% catalyst amount, 190°C temperature, 15:1 methanol to oil molar ratio and 1 h 21 min reaction time. At the optimum condition, the ME content was 80.98%, which is well within the predicted value of the model. Catalyst regeneration studies indicate that the catalyst performance is sustained after two cycles.
We have calculated the vibrational frequencies of clusters of atoms from the first principles by using the density-functional theory in the local density approximation (LDA). We are also able to calculate the electronic binding energy for all of the clusters of atoms from the optimized structure. We have made clusters of BanOm (n, m=1-6) and have determined the bond lengths, vibrational frequencies as well as intensities in each case. We find that the peroxide cluster BaO2 occurs with the O-O vibrational frequency of 836.3 cm(-1). We also find that a glass network occurs in the material which explains the vibrational frequency of 67 cm(-1). The calculated values agree with those measured from the Raman spectra of barium peroxide and Ba-B-oxide glass. We have calculated the vibrational frequencies of BaO4, GeO4 and SiO4 each in tetrahedral configuration and find that the vibrational frequencies in these systems depend on the inverse square root of the atomic mass.
We present results from the OP3 campaign in Sabah during 2008 that allow us to study the impact of local emission changes over Borneo on atmospheric composition at the regional and wider scale. OP3 constituent data provide an important constraint on model performance. Treatment of boundary layer processes is highlighted as an important area of model uncertainty. Model studies of land-use change confirm earlier work, indicating that further changes to intensive oil palm agriculture in South East Asia, and the tropics in general, could have important impacts on air quality, with the biggest factor being the concomitant changes in NO(x) emissions. With the model scenarios used here, local increases in ozone of around 50 per cent could occur. We also report measurements of short-lived brominated compounds around Sabah suggesting that oceanic (and, especially, coastal) emission sources dominate locally. The concentration of bromine in short-lived halocarbons measured at the surface during OP3 amounted to about 7 ppt, setting an upper limit on the amount of these species that can reach the lower stratosphere.
This paper reports measurements of land-atmosphere fluxes of sensible and latent heat, momentum, CO(2), volatile organic compounds (VOCs), NO, NO(2), N(2)O and O(3) over a 30 m high rainforest canopy and a 12 m high oil palm plantation in the same region of Sabah in Borneo between April and July 2008. The daytime maximum CO(2) flux to the two canopies differs by approximately a factor of 2, 1200 mg C m(-2) h(-1) for the oil palm and 700 mg C m(-2) h(-1) for the rainforest, with the oil palm plantation showing a substantially greater quantum efficiency. Total VOC emissions are also larger over the oil palm than over the rainforest by a factor of 3. Emissions of isoprene from the oil palm canopy represented 80 per cent of the VOC emissions and exceeded those over the rainforest in similar light and temperature conditions by on average a factor of 5. Substantial emissions of estragole (1-allyl-4-methoxybenzene) from the oil palm plantation were detected and no trace of this VOC was detected in or above the rainforest. Deposition velocities for O(3) to the rainforest were a factor of 2 larger than over oil palm. Emissions of nitrous oxide were larger from the soils of the oil palm plantation than from the soils of the rainforest by approximately 25 per cent. It is clear from the measurements that the large change in the species composition generated by replacing rainforest with oil palm leads to profound changes in the net exchange of most of the trace gases measured, and thus on the chemical composition of the boundary layer over these surfaces.
We report measurements of atmospheric composition over a tropical rainforest and over a nearby oil palm plantation in Sabah, Borneo. The primary vegetation in each of the two landscapes emits very different amounts and kinds of volatile organic compounds (VOCs), resulting in distinctive VOC fingerprints in the atmospheric boundary layer for both landscapes. VOCs over the Borneo rainforest are dominated by isoprene and its oxidation products, with a significant additional contribution from monoterpenes. Rather than consuming the main atmospheric oxidant, OH, these high concentrations of VOCs appear to maintain OH, as has been observed previously over Amazonia. The boundary-layer characteristics and mixing ratios of VOCs observed over the Borneo rainforest are different to those measured previously over Amazonia. Compared with the Bornean rainforest, air over the oil palm plantation contains much more isoprene, monoterpenes are relatively less important, and the flower scent, estragole, is prominent. Concentrations of nitrogen oxides are greater above the agro-industrial oil palm landscape than over the rainforest, and this leads to changes in some secondary pollutant mixing ratios (but not, currently, differences in ozone). Secondary organic aerosol over both landscapes shows a significant contribution from isoprene. Primary biological aerosol dominates the super-micrometre aerosol over the rainforest and is likely to be sensitive to land-use change, since the fungal source of the bioaerosol is closely linked to above-ground biodiversity.
The granulation process in palm oil mill effluent using calcium oxide-cement kiln dust (CaO-CKD) provides an attractive and cost effective treatment option. In this study the efficiency of CaO-CKD at doses of 1.5-20 g/l was tested in batch experiments and found that 10 g of CaO/l caused the greatest degradation of VFA, butyrate and acetate. An upflow anaerobic sludge blanket (UASB) reactor was operated continuously at 35°C for 150 days to investigate the effect of CaO-CKD on sludge granulation and methanogenesis during start-up. The treatment of POME emphasized the influence of varying organic loading rates (OLR). Up to 94.9% of COD was removed when the reactor was fed with the 15.5-65.5 g-CODg/l at an OLR of 4.5-12.5 kg-COD/m(3)d, suggesting the feasibility of using CaO in an UASB process to treat POME. The ratio of volatile solids/total solids (VS/TS) and volatile fatty acids in the anaerobic sludge in the UASB reactor decreased significantly after long-term operation due to the precipitation of calcium carbonate in the granules. Granulation and methanogenesis decreased with an increase in the influent CaO-CKD concentration.
Graphene has attracted much attention from researchers due to its interesting mechanical, electrochemical, and electronic properties. It has many potential applications such as polymer filler, sensor, energy conversion, and energy storage devices. Graphene-based nanocomposites are under an intense spotlight amongst researchers. A large amount of graphene is required for preparation of such samples. Lately, graphene-based materials have been the target for fundamental life science investigations. Despite graphene being a much sought-after raw material, the drawbacks in the preparation of graphene are that it is a challenge amongst researchers to produce this material in a scalable quantity and that there is a concern about its safety. Thus, a simple and efficient method for the preparation of graphene oxide (GO) is greatly desired to address these problems. In this work, one-pot chemical oxidation of graphite was carried out at room temperature for the preparation of large-area GO with ~100% conversion. This high-conversion preparation of large-area GO was achieved using a simplified Hummer's method from large graphite flakes (an average flake size of 500 μm). It was found that a high degree of oxidation of graphite could be realized by stirring graphite in a mixture of acids and potassium permanganate, resulting in GO with large lateral dimension and area, which could reach up to 120 μm and ~8000 μm(2), respectively. The simplified Hummer's method provides a facile approach for the preparation of large-area GO.
This paper reports the design of an electronic nose (E-nose) prototype for reliable measurement and correct classification of beverages. The prototype was developed and fabricated in the laboratory using commercially available metal oxide gas sensors and a temperature sensor. The repeatability, reproducibility and discriminative ability of the developed E-nose prototype were tested on odors emanating from different beverages such as blackcurrant juice, mango juice and orange juice, respectively. Repeated measurements of three beverages showed very high correlation (r > 0.97) between the same beverages to verify the repeatability. The prototype also produced highly correlated patterns (r > 0.97) in the measurement of beverages using different sensor batches to verify its reproducibility. The E-nose prototype also possessed good discriminative ability whereby it was able to produce different patterns for different beverages, different milk heat treatments (ultra high temperature, pasteurization) and fresh and spoiled milks. The discriminative ability of the E-nose was evaluated using Principal Component Analysis and a Multi Layer Perception Neural Network, with both methods showing good classification results.
Photopyroelectric (PPE) spectroscopy is a nondestructive tool that is used to study the optical properties of the ceramics (ZnO + 0.4MnO(2) + 0.4Co(3)O(4) + xV(2)O(5)), x = 0-1 mol%. Wavelength of incident light, modulated at 10 Hz, was in the range of 300-800 nm. PPE spectrum with reference to the doping level and sintering temperature is discussed. Optical energy band-gap (E(g)) was 2.11 eV for 0.3 mol% V(2)O(5) at a sintering temperature of 1025 °C as determined from the plot (ρhυ)(2)versushυ. With a further increase in V(2)O(5), the value of E(g) was found to be 2.59 eV. Steepness factor 'σ(A)' and 'σ(B)', which characterize the slope of exponential optical absorption, is discussed with reference to the variation of E(g). XRD, SEM and EDAX are also used for characterization of the ceramic. For this ceramic, the maximum relative density and grain size was observed to be 91.8% and 9.5 μm, respectively.
Heavy metal oxide glasses, containing bismuth and/or lead in their glass structure are new alternatives for rare eart (RE) doped hosts. Hence, the study of the structure of these vitreous systems is of great interest for science and technology. In this research work, GeO(2)-PbO-Bi(2)O(3) glass host doped with Er(3+)/Yb(3+) ions was synthesized by a conventional melt quenching method. The Fourier transform infrared (FTIR) results showed that PbO and Bi(2)O(3) participate with PbO(4) tetragonal pyramids and strongly distort BiO(6) octahedral units in the glass network, which subsequently act as modifiers in glass structure. These results also confirmed the existence of both four and six coordination of germanium oxide in glass matrix.
This manuscript reports on the physical properties and optical band gap of five samples of soda lime silicate (SLS) glass combined with zinc oxide (ZnO) that were prepared by a melting and quenching process. To understand the role of ZnO in this glass structure, the density, molar volume and optical band gaps were investigated. The density and absorption spectra in the Ultra-Violet-Visible (UV-Visible) region were recorded at room temperature. The results show that the densities of the glass samples increased as the ZnO weight percentage increased. The molar volume of the glasses shows the same trend as the density: the molar volume increased as the ZnO content increased. The optical band gaps were calculated from the absorption edge, and it was found that the optical band gap decreased from 3.20 to 2.32 eV as the ZnO concentration increased.
We report on a recycling project in which α-Al(2)O(3) was produced from aluminum cans because no such work has been reported in literature. Heated aluminum cans were mixed with 8.0 M of H(2)SO(4) solution to form an Al(2)(SO(4))(3) solution. The Al(2)(SO(4))(3) salt was contained in a white semi-liquid solution with excess H(2)SO(4); some unreacted aluminum pieces were also present. The solution was filtered and mixed with ethanol in a ratio of 2:3, to form a white solid of Al(2)(SO(4))(3)·18H(2)O. The Al(2)(SO(4))(3)·18H(2)O was calcined in an electrical furnace for 3 h at temperatures of 400-1400 °C. The heating and cooling rates were 10 °C /min. XRD was used to investigate the phase changes at different temperatures and XRF was used to determine the elemental composition in the alumina produced. A series of different alumina compositions, made by repeated dehydration and desulfonation of the Al(2)(SO(4))(3)·18H(2)O, is reported. All transitional alumina phases produced at low temperatures were converted to α-Al(2)O(3) at high temperatures. The X-ray diffraction results indicated that the α-Al(2)O(3) phase was realized when the calcination temperature was at 1200 °C or higher.
Herein, an efficient epoxidation of 1-nonene is described. In a simple epoxidation system, commercially available Novozym 435, an immobilized Candida antarctica lipase B, and hydrogen peroxide (H(2)O(2)) were utilized to facilitate the in situ oxidation of phenylacetic acid to the corresponding peroxy acid which then reacted with 1-nonene to give 1-nonene oxide with high yield and selectivity. The aliphatic terminal alkene was epoxidised efficiently in chloroform to give an excellent yield (97%-99%) under the optimum reaction conditions, including temperature (35 °C), initial H(2)O(2) concentration (30%), H(2)O(2) amount (4.4 mmol), H(2)O(2) addition rate (one step), acid amount (8.8 mmol), and stirring speed (250 rpm). Interestingly, the enzyme was stable under the single-step addition of H(2)O(2) with a catalytic activity of 190.0 Ug-1. The entire epoxidation process was carried out within 12 h using a conventional water bath shaker.
This study is the first to demonstrate dimensional optimization of nanowire-complementary metal-oxide-semiconductor inverter. Noise margins and inflection voltage of transfer characteristics are used as limiting factors in this optimization. Results indicate that optimization depends on both dimensions ratio and digital voltage level (Vdd). Diameter optimization reveals that when Vdd increases, the optimized value of (Dp/Dn) decreases. Channel length optimization results show that when Vdd increases, the optimized value of Ln decreases and that of (Lp/Ln) increases. Dimension ratio optimization reveals that when Vdd increases, the optimized value of Kp/Kn decreases, and silicon nanowire transistor with suitable dimensions (higher Dp and Ln with lower Lp and Dn) can be fabricated.