Chun-Yu Chiu

Combined photolysis and catalytic ozonation of dimethyl phthalate in a high-gravity rotating packed bed

In this study, a high-gravity rotating packed bed (HGRPB) was used as a catalytic ozonation reactor to decompose dimethyl phthalate (DMP), an endocrine disrupting chemical commonly encountered. The HGRPB is an effective gas-liquid mixing equipment which can enhance the ozone mass transfer coefficient. Platinum-containing catalyst (Pt/-Al2O3) of Dash 220N and ultra violet (UV) lamp were combined in the high-gravity ozonation (HG-OZ) system to enhance the self-decomposition of molecular ozone in liquid to form highly reactive radical species. Different combinations of HG-OZ with Dash 220N and UV for the degradation of DMP were tested. These include HG-OZ, HG catalytic OZ (HG-Pt-OZ), HG photolysis OZ (HG-UV-OZ) and HG-UV-Pt-OZ. The result indicated that all the above four ozonation processes result in significant decomposition of DMP and mineralization of total organic carbon (TOC) at the applied ozone dosage per volume of liquid sample of 1.2gL(-1). The UV and Pt/gamma-Al2O3 combined in HG-OZ can enhance the TOC mineralization efficiency (eta(TOC)) to 56% (via HG-UV-OZ) and 57% (via HG-Pt-OZ), respectively, while only 45% with ozone only. The process of HG-UV-Pt-OZ offers the highest eta(TOC) of about 68%.

Kinetics and equilibrium of desorption removal of copper from magnetic polymer adsorbent.

This study examined the desorption of copper ions, which were adsorbed on the magnetic polymer adsorbent (MPA) of polyvinyl acetate-iminodiacetic acid (M-PVAC-IDA), by ethylenediaminetetraacetic acid (EDTA). Stage-wise desorptions were applied to remove the Cu(II) ions from the Cu(II) adsorbed M-PVAC-IDA (A-M-PVAC-IDA). About seven desorption runs were needed to regenerate the A-M-PVAC-IDA. The Cu(II) desorbed M-PVAC-IDA (D-M-PVAC-IDA) was then reused to adsorb the Cu(II) ions from the Cu(II) ions-containing solution. The cyclic adsorption and desorption operations (CADOs) were performed to further elucidate the kinetics and equilibria of the desorption system of EDTA/A-M-PVAC-IDA and the adsorption system of Cu(II)-containing solution/D-M-PVAC-IDA. Two simple kinetic models, the pseudo-first-order equation and pseudo-second-order equation, were employed to simulate the kinetic behaviors of adsorption and desorption. With respect to the kinetics of adsorption behavior, the simulated results by both kinetic models exhibit good agreement with the experimental data. However, the adsorption capacities (q(e)) estimated by the pseudo-first-order equation are more accurate in comparison with those simulated by the pseudo-second-order equation. As for the desorption kinetics, the examination of correlation coefficients of model fittings of data shows that the pseudo-first-order kinetic model gives the better agreement for the cases with different initial solid-phase concentrations and can accurately compute the equilibrium concentrations of solid-phase. The values of q(e) after CADOs are consistent with the predicted results via the previous work, evidencing that the adsorption behavior and the characteristics of the regenerated adsorbent of D-M-PVAC-IDA were not altered. In the experiments of desorbing copper ions and CADOs, the desorption isotherm was set up. The Freundlich and Langmuir adsorption (or desorption) isotherms were used to simulate the equilibrium of desorption. The results indicate that the Freundlich equation shows better agreement with the experimental data than the Langmuir equation. The information thus obtained is useful for the better use of M-PVAC-IDA on the removal of heavy mental ions of Cu(II) from the Cu(II) ion-containing water solution with the consideration of its regeneration.

Decomposition of 2-naphthalenesulfonate in aqueous solution by ozonation with UV radiation

This study investigates the ozonation of 2-naphthalenesulfonate (2-NS) combined with ultraviolet (UV) radiation. Naphthalenesulfonic acids are of importance as dye intermediates for the dye and textile auxiliary industries. Its derivatives, such as 2-NS, have been found in rivers and tannery effluents causing pollution problems. Thus, the 2-NS is of concern for the aquatic pollution control especially in the surface and waste waters. Ozonation combined with UV radiation is employed for the removal of 2-NS in the aqueous solution. Semibatch ozonation experiments were proceeded under different reaction conditions to study the effects of ozone dosage and UV radiation on the oxidation of 2-NS. The concentrations of 2-NS and sulfate are analyzed at specified time intervals to elucidate the decomposition of 2-NS. In addition, values of pH and oxidation reduction potential are continuously measured in the course of experiments. Total organic carbon is chosen as a mineralization index of the ozonation of 2-NS. The mineralization of 2-NS via the ozonation is remarkably enhanced by the UV radiation. These results can provide useful information for the proper removal of 2-NS in the aqueous solution by the ozonation with UV radiation.

Pt-catalyzed ozonation of aqueous phenol solution using high-gravity rotating packed bed

In this study, a high-gravity rotating packed bed (HGRPB or HG) was used as a catalytic ozonation (Cat-OZ) reactor to decompose phenol. The operation of HGRPB system was carried out in a semi-batch apparatus which combines two major parts, namely the rotating packed bed (RPB) and photo-reactor (PR). The high rotating speed of RPB can give a high volumetric gas-liquid mass transfer coefficient with one or two orders of magnitude higher than those in the conventional packed beds. The platinum-containing catalyst (Dash 220N, Pt/gamma-Al(2)O(3)) and activated alumina (gamma-Al(2)O(3)) were packed in the RPB respectively to adsorb molecular ozone and the target pollutant of phenol on the surface to catalyze the oxidation of phenol. An ultra violet (UV) lamp (applicable wavelength lambda=200-280 nm) was installed in the PR to enhance the self-decomposition of molecular ozone in water to form high reactive radical species. Different combinations of advanced oxidation processes (AOPs) with the HGRPB for the degradation of phenol were tested. These included high-gravity OZ (HG-OZ), HG catalytic OZ (HG-Cat-OZ), HG photolysis OZ (HG-UV-OZ) and HG-Cat-OZ with UV (HG-Cat-UV-OZ). The decomposition efficiency of total organic compound (eta(TOC)) of HG-UV-OZ with power of UV (P(UV)) of 16W is 54% at applied dosage of ozone per volume sample m(A,in)=1200 mg L(-1) (reaction time t=20 min), while that of HG-OZ without the UV irradiation is 24%. After 80 min oxidation (m(A,in)=4800 mg L(-1)), the eta(TOC) of HG-UV-OZ is as high as 94% compared to 82% of HG-OZ process. The values of eta(TOC) for HG-Cat-OZ process with m(S)=42 g are 56% and 87% at m(A,in)=1200 and 4800 mg L(-1), respectively. By increasing the catalyst mass to 77 g, the eta(TOC) for the HG-Cat-OZ process reaches 71% and 90% at m(A,in)=1200 and 4800 mg L(-1), respectively. The introduction of Pt/gamma-Al(2)O(3) as well as UV irradiation in the HG-OZ process can enhance the eta(TOC) of phenol significantly, while gamma-Al(2)O(3) exhibits no significant effect on eta(TOC). For the HG-Cat-UV-OZ process with m(S)=42 g, the values of eta(TOC) are 60% and 94% at m(A,in)=1200 and 4800 mg L(-1), respectively. Note that the decomposition of TOC via HG-UV-OZ is already vigorous. Thus, the enhancing effect of catalyst on eta(TOC) is minor.

Dynamic behavior of ozonation with pollutant in a countercurrent bubble column with oxygen mass transfer

The dynamic behavior of ozonation with pollutants in a countercurrent bubble column is studied for the model establishment. Bubble columns have been widely used for an ozonation system in the plants and laboratories. In addition, a countercurrent bubble column has been commonly recommended than a cocurrent one because it has a higher ozone transfer efficiency. Therefore, the investigation of this paper focuses on the countercurrent bubble column. As an ozonation process starts, the gas mixture of ozone and oxygen is introduced into the bottom of a column, and then transferred into the liquid. The pollutants in the wastewater are eliminated subsequently via oxidation by the dissolved ozone. There certainly exists a temporary and unsteady period before the ozonation system reaches steady state. However, available ozonation models employed to describe ozone and pollutant profiles have commonly been developed for steady state. The treating qualities of wastewater in the early stage of ozonation are usually not predicted, and the time required for the steady-state establishment remains to be determined. Moreover, oxygen mass transfer is usually neglected in previous ozonation models so that the increase of dissolved oxygen is uncertain. These information is desirable for the proper design and operation of ozonation system in a bubble column. Thus, the aim of this study is to model and investigate the dynamic processes of ozonation with pollutants including oxygen mass transfer. The dynamic axial dispersion model proposed is employed to predict the variation of the ozone, pollutant, and oxygen concentrations profiles. The validity of the model was demonstrated by comparing the predicted results with the experimental data. The o-cresol was chosen as the model pollutant. The temporal concentration variations of the residual o-cresol and dissolved oxygen in the effluent liquid, and the off-gas ozone in the free volume were measured accordingly. Furthermore, the variation of the enhancement factor of ozone and the amount of off-gas were predicted. Note that it usually needs 2-5 hydraulic retention times to approach steady state under the conditions of this study. Further, the effects of dimensionless system parameters on the performance of the ozonation processes are examined. As a result, the proposed dynamic model of ozonation with pollutants is useful for proper prediction of the variables of an ozonation system in a countercurrent bubble column.

A Dynamic Model of Ozone Disinfection in a Bubble Column with Oxygen Mass Transfer

The dynamic process of disinfection with ozone in a bubble column is studied for model establishment. Bubble columns have been widely used for ozone disinfection in plants and laboratories. Ozone is produced by passing oxygen-enriched gas through an ozone generator, and introduced into the bottom of a column equipped with a gas-diffuser. There certainly exists a temporary and unsteady period before the ozone disinfection system reaches steady state. Available ozone disinfection models employed to describe dissolved ozone and surviving microorganism profiles have commonly been developed for steady state. Moreover, oxygen maxx transfer has usually been neglected in previous ozone disinfection models. However, this information is desirable for the proper operation of ozone disinfection in a bubble column. Thus, the objective of this study was to model and investigate the dynamic ozone disinfection process in a bubble column with oxygen mass transfer. A dynamic axial dispersion model is proposed and was employed to predict the variation of the ozone, microorganism and oxygen concentrations along the column. The results of prediction were obtained based on the conditions of Marinas et al. (1993). E. coli was chosen as the model microorganism. The dynamic model of ozone inactivation is useful for proper prediction of the variables of an ozone disinfection system in a bubble column.

Adsorption Removal of Environmental Hormones of Dimethyl Phthalate Using Novel Magnetic Adsorbent.

Magnetic polyvinyl alcohol adsorbent M-PVAL was employed to remove and concentrate dimethyl phthalate DMP. The M-PVAL was prepared after sequential syntheses of magnetic Fe3O4 (M) and polyvinyl acetate (M-PVAC). The saturated magnetizations of M, M-PVAC, and M-PVAL are 57.2, 26.0, and 43.2 emu g−1 with superparamagnetism, respectively. The average size of M-PVAL by number is 0.75 μm in micro size. Adsorption experiments include three cases: (1) adjustment of initial pH (pH0) of solution to 5, (2) no adjustment of pH0 with value in 6.04–6.64, and (3) adjusted pH0 = 7. The corresponding saturated amounts of adsorption of unimolecular layer of Langmuir isotherm are 4.01, 5.21, and 4.22 mg g−1, respectively. Values of heterogeneity factor of Freundlich isotherm are 2.59, 2.19, and 2.59 which are greater than 1, revealing the favorable adsorption of DMP/M-PVAL system. Values of adsorption activation energy per mole of Dubinin-Radushkevich isotherm are, respectively, of low values of 7.04, 6.48, and 7.19 kJ mol−1, indicating the natural occurring of the adsorption process studied. The tiny size of adsorbent makes the adsorption take place easily while its superparamagnetism is beneficial for the separation and recovery of micro adsorbent from liquid by applying magnetic field after completion of adsorption.

Ozone Mass Transfer with Combined Effects of Ozone Decomposition and Reaction with Pollutants in a Semibatch Stirred Vessel

The mathematical models for a semibatch stirred gas-liquid contactor proposed by Anselmi et al. (1984, 1985) are extended to described the mass transfer of ozone absorption, decomposition and reaction with pollutants in aqueous solution with the decomposition and reaction rate expressions of general reaction orders (not necessarily integers) taking into consideration the effects of ozone decomposition and reactions on absorption. Four system equations are employed to describe the ozone (A) concentrations in the bulk liquid (CALb), the hold-up gas (CAGi), and the outlet gas in the free volume above the liquid surface (CAGe), and the pollutant (B) concentration in the bulk liquid (CBTLb), respectively. The combined effects of ozone decomposition and reaction with pollutant on the mass transfer, which are reflected by the enhancement factor (Er) defined as the ratio of mass absorbed per unit area in time t with chemical reactions to that without chemical reactions or of the purely physical absorption, are considered in the refined model. Furthermore, the model also takes into account the variation of Er with CALb and CBTLb, which vary with time during the course of gas-liquid contacting. Comparison of the predicted values of concentrations of the proposed model in simplified from with the experimental data of Anselmi et al (1985) indicates good agreement. For ozonation systems with high reaction rates(for example, ozonation of o-cresol investigated by Beltran et al. (1990)), the enhancement factors are large and cause significant influence on the mass transfer of the ozone and pollutant.

Decomposition and Mineralization of Dimethyl Phthalate in an Aqueous Solution by Wet Oxidation

Dimethyl phthalate (DMP) was treated via wet oxygen oxidation process (WOP). The decomposition efficiency η DMP of DMP and mineralization efficiency η TOC of total organic carbons were measured to evaluate the effects of operation parameters on the performance of WOP. The results revealed that reaction temperature T is the most affecting factor, with a higher T offering higher η DMP and η TOC as expected. The η DMP increases as rotating speed increases from 300 to 500 rpm with stirring enhancement of gas liquid mass transfer. However, it exhibits reduction effect at 700 rpm due to purging of dissolved oxygen by overstirring. Regarding the effects of pressure P T, a higher P T provides more oxygen for the forward reaction with DMP, while overhigh P T increases the absorption of gaseous products such as CO2 and decomposes short-chain hydrocarbon fragments back into the solution thus hindering the forward reaction. For the tested P T of 2.41 to 3.45 MPa, the results indicated that 2.41 MPa is appropriate. A longer reaction time of course gives better performance. At 500 rpm, 483 K, 2.41 MPa, and 180 min, the η DMP and η TOC are 93 and 36%, respectively.