Hiroshi Bandow

A two-step continuous ultrasound assisted production of biodiesel fuel from waste cooking oils: A practical and economical approach to produce high quality biodiesel fuel

A transesterification reaction of waste cooking oils (WCO) with methanol in the presence of a potassium hydroxide catalyst was performed in a continuous ultrasonic reactor of low-frequency 20 kHz with input capacity of 1 kW, in a two-step process. For the first step, the transesterification was carried out with the molar ratio of methanol to WCO of 2.5:1, and the amount of catalyst 0.7 wt.%. The yield of fatty acid methyl esters (FAME) was about 81%. A yield of FAME of around 99% was attained in the second step with the molar ratio of methanol to initial WCO of 1.5:1, and the amount of catalyst 0.3 wt.%. The FAME yield was extremely high even at the short residence time of the reactants in the ultrasonic reactor (less than 1 min for the two steps) at ambient temperature, and the total amount of time required to produce biodiesel was 15h. The quality of the final biodiesel product meets the standards JIS K2390 and EN 14214 for biodiesel fuel.

Formation of noble metal particles by ultrasonic irradiation

Abstract It was found that sonochemically prepared metal particles such as Ag, Pd, Au, Pt and Rh are of nanometer size with a fairly narrow distribution (e.g., about 5 nm for Pd particles obtained from a 1.0 mM Pd(II) in polyethylene glycol monostearate solution). We have suggested three different reduction pathways under sonication: (i) reduction by H atoms, (ii) reduction by secondary reducing radicals formed by hydrogen abstraction from organic additives with OH radicals and H atoms, (iii) reduction by radicals formed from pyrolysis of the additives at the interfacial region between cavitation bubbles and the bulk solution. The reduction of Ag(I) and Pt(II) mainly proceeds through reaction pathway (ii). In the cases of Pd(II) and Au(III), the reductions mainly proceed through reaction pathway (iii). The reduction of Rh(III) was not achieved under the same conditions; however, by the addition of sodium formate, reduction occurred and the preparation of Rh particles succeeded.

Effect of reaction vessel diameter on sonochemical efficiency and cavitation dynamics.

The influence of reaction vessel diameter on the sonochemical yield was investigated by using reaction vessels with five different diameters. It was revealed that the formation of H(2)O(2) and chloride ion, from the sonolysis of pure water and 1,2,4-trichlorobenzene aqueous solution, was affected by the reaction vessel diameter. That is, these yields increased as the reaction vessel diameter increased up to ø 90 mm and then decreased over ø 90 mm. From the analyses of the measurement of sonochemiluminescence and the calorimetry, it was suggested that active cavitation bubbles were formed at certain zones. In the case of a larger diameter reaction vessel, it was suggested that bubble nuclei that have not grown up to the resonance size, escaped from the sonication zone to the non-sonication zone and dissolved away. As a result, the number of active cavitation bubbles and the yields of H(2)O(2) and chloride ion would decrease in the case of a larger diameter reaction vessel.

Numerical study of the atmospheric input of anthropogenic total nitrate to the marginal seas in the western North Pacific region

[1] Atmospheric input of anthropogenic total nitrate to marginal seas in the western North Pacific region was simulated using a regional chemical transport model over East Asia based on year-to-year emission estimates during 1980-2003. Seasonal cycles and concentration levels of gas and aerosol were examined using observation data from various studies. The model simulated total nitrate deposition over the East China Sea (ECS) as 140 GgN/yr, which is the same order of the annual river discharge from the Yangtze River. The ratio of dry and wet deposition over ECS was obtained as approximately 6: 4. Total nitrate deposition over ECS corresponds to 3.2% (N base) of total NO x emission in China. The total deposition at present is three times larger than that of 1980, corresponding with increased NO x emissions.

Determination of trace amounts of urea by using flow injection with chemiluminescence detection

Reaction between urea and hypobromite in alkaline solution was found to produce chemiluminescence with a maximum wavelength at 510 nm. A simple chemiluminescence detection method was used for the determination of urea in human urine and natural aqueous samples, which combined this chemiluminescence reaction with a flow injection analysis system. The relative standard deviation for 5 x 10(-7) mol dm-3 urea is 1.9% (n = 6), and the detection limit is 9.0 x 10(-8) mol dm-3 (3Sr). As this chemiluminescence reaction is very fast, a double concentric tube mixer connected directly to the chemiluminescence cell was used to mix urea solution and hypobromite solution. Alkylamines, carboxylic acids and most amino acids do not interfere in the determination. Ammonium ion interferes, but the sensitivity for ammonium ion is only 1% of that for urea. The interference from ammonium ion was removed sufficiently by using an on-line cation-exchange column.

Effect of carbon tetrachloride on sonochemical decomposition of methyl orange in water

Two types of sonicators were used for the sonochemical decomposition of methyl orange (MO) in the presence and absence of carbon tetrachloride (CCl4): One is a 45kHz ultrasonic cleaning bath (a low intensity sonicator) and the other is a 200kHz ultrasonic reactor (a high intensity sonicator). It was clearly confirmed that the rates of the sonochemical decomposition of MO increased with increasing the concentration of CCl4 in both sonicators. The enhancement effect of CCl4 was much higher in the high intensity sonicator than in the low intensity one: by the addition of 100ppm of CCl4, the decomposition ratio of MO with the high intensity sonicator became 41 times larger, while that with the low intensity sonicator became 4.8 times larger. Based on the obtained results, it was suggested that the formed cavitation phenomenon was different between sonicators. It was also suggested that the sonochemical decomposition of MO in the presence of CCl4 would be useful to evaluate the sonochemical efficiency, because the rate of MO decomposition can be effectively enhanced by the sonolysis of CCl4.

Sonochemical decomposition of organic acids in aqueous solution: Understanding of molecular behavior during cavitation by the analysis of a heterogeneous reaction kinetics model

The sonochemical decomposition of a low concentration of butyric acid was performed in an aqueous solution by use of 200 kHz ultrasound to discuss the reaction kinetics and molecular behavior during cavitation. Taking into account a Langmuir-type adsorption model, we propose a heterogeneous reaction kinetics model, which is based on the local reaction zone at the interface region of the cavitation bubbles, where the adsorption and desorption of butyric acid molecules from the bulk solution occur during bubble oscillation and then the existing molecules inside the local reaction zone are finally decomposed. To confirm our proposed kinetics model, the rates of decomposition were investigated as a function of the initial concentration of butyric acids in the different pH solutions. It was confirmed that our model could be reasonably applied to explain the obtained results and the pseudo rate constant (k) and the equilibrium constant (K) were able to be calculated: k is 8.0 microM min(-1) (pH 2) and 3.5 microM min(-1) (pH 10), and K is 5.7 x 10(-3) microM(-1) (pH 2) and 8.0 x 10(-3) microM(-1) (pH 10), respectively. By the analysis of the obtained K values, it was clear that the ionized organic acid molecules are relatively difficult to accumulate at the reaction zone, because of their lower hydrophobicity compared with that of the neutral ones. The results obtained in the sonochemical decomposition of benzoic acid were also able to be analyzed with the proposed kinetics model. In addition, we proposed an opinion toward the interpretation of a Langmuir-type adsorption model which has often been applied to explain heterogeneous reaction systems.

Transport of Atmospheric Pollutants from East Asia

Air-borne measurements of air pollutants transported from northeast Asia to Japan and the Pacific Ocean were carried out three times from 1996 to 1999 over the seas between Japan and Asian Continent. Those campaigns were named PEACAMPOT II under auspices of the IGAC/APARE program. A transport pattern of a highly polluted air mass from central China was found. Such air mass was driven by the quick movement of low pressure traveling from Taiwan area to the northeast of Japan. This finding supported well the results of modeling studies for long-range transport of atmospheric pollutants from East Asia.

Difference in amounts and composition of dew from different types of dew collectors

Dew was collected using several kinds of collectors at the same time, and the composition was compared. The volumes per unit surface areas of dew formed were different based on the types of collectors. It is found that the amounts of the ions, which in part come from gaseous substances, such as organic acids, nitrous acid, etc., per unit area in dew increase with dew volume per unit surface area. On the other hand, chloride, nitrate, sodium, potassium and magnesium which come from only particles showed no variation with the dew volume per unit surface area. These results suggest that the composition of dew varied by the dew volume per unit surface area formed in the different collectors. Dew is usually collected on a polytetrafluoroethylene (PTFE) sheet. The above result suggests that the dew concentration on the PTFE sheet does not represent the real dew concentration on various materials, such as leaves, cars, roofs, road, etc. To determine the real concentration of dew on a material, the material itself has to be usedas a collector. The PTFE sheet could be used as a standard dew sampler forcomparison of dew formed at various places.

Characteristics of the abundance of polychlorinated dibenzo-p-dioxin and dibenzofurans, and dioxin-like polychlorinated biphenyls in sediment samples from selected Asian regions in Can Gio, Southern Vietnam and Osaka, Japan.

The levels of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) were determined in sediment samples from Can Gio, South Vietnam, and Osaka, Japan. Can Gio is known for the defoliation of its mangrove forests by aerial spraying with Agent Orange during the Vietnam War, whereas Osaka is renowned for a PCDD/PCDF pollution accident at a municipal solid-waste incinerator. For comparison, we also analyzed PCDD/PCDFs and DL-PCBs in sediment samples from Hue and Hanoi, Vietnam. The toxic equivalent quantity (TEQ) values in Can Gio were as high as those in Hue, Hanoi, and suburban areas of Osaka, but much lower than those in urban areas of Osaka. The proportion of the World Health Organization (WHO)-TEQ value contributed by 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD) in Can Gio was approximately 30%, higher than the values in the other sample areas. These data suggest that residual sedimentary TCDD that originated from aerial spraying of Agent Orange occur in only low concentrations in Can Gio. The main contributors to WHO-TEQ values in Can Gio are natural sources, as in Hue. In contrast, commercial PCBs are the dominant contributors to WHO-TEQ values in Hanoi. In Osaka, agrochemicals used in rice cultivation, the incineration of solid waste, and commercial PCBs equally contributed to WHO-TEQ values at suburban locations. The dumping of incinerator-related materials and/or the inadequate management of commercial PCBs have resulted in significantly elevated WHO-TEQ values of 240-370 ng kg(-1)dw at urban locations in Osaka.