Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

Mathematical model for photocatalytic destruction of organic contaminants in air

Photocatalytic oxidation (PCO) was investigated in a bench-scale reactor for the abatement of two airborne organic contaminants: toluene and ethanol. A mathematical model that includes the impacts of light intensity, initial contaminant concentration, catalyst thickness, and relative humidity (RH) on the degradation of organic contaminants in a photocatalytic reactor was developed to describe this process. The commercially available catalyst Degussa-PtTiO2 was selected to compare with the MTU-PtTiO2-350 catalyst, which was synthesized by the sol-gel process, platinized, and calcined at 350 degrees C. For toluene removal using the MTU-PtTiO2-350 catalyst, the degradation rate increased with increases in light intensity from 0.2 to 2.2 mW/cm2 and in catalyst thickness from 0.00037 to 0.00361 cm. However, further increases in light intensity and catalyst thickness had only slight effect on the toluene degradation rate. Increasing the initial concentration from 6.29 to 127.9 microg/L and the RH from 10 to 85% resulted in decreases in the toluene degradation rate. For ethanol removal using the MTU-PtTiO2-350 catalyst, the degradation rate increased more rapidly with an increase in RH from 17 to 56%; the RH had little effect on the ethanol degradation rate while it further increased from 56% to 82%. We discuss applicability of the model to estimate the influence of process variables and to evaluate photocatalyst performance.     

PVDF ultrafiltration membranes of controlled performance via blending PVDF-g-PEGMA copolymer synthesized under different reaction times

PVDF blended different graft ratio of PVDF-g-PEGMA were systematically studied. Tuning the amphiphilic copolymer synthesis time to control membrane performance. The PVDF membrane with PVDF-g-PEGMA at 19 h possesses most surface oxygen content. The synthesis time of PVDF-g-PEGMA at 9 h is good for high flux UF membrane. Polyvinylidene fluoride grafted with poly(ethylene glycol) methyl ether methacrylate (PVDF-g-PEGMA) was synthesized using atomic transfer radical polymerization (ATRP) at different reaction times (9 h, 19 h, and 29 h). The corresponding conversion rates were 10%, 20% and 30%, respectively. PVDF was blended with the copolymer mixture containing PVDF-g-PEGMA, solvent and residual PEGMA under different reaction times. In this study, we explored the effect of the copolymer mixture additives with different synthesis times on cast membrane performance. Increasing the reaction time of PVDF-g-PEGMA causes more PVDF-g-PEGMA and less residual PEGMA to be found in the casting solution. Incremental PVDF-g-PEGMA can dramatically increase the viscosity of the casting solution. An overly high viscosity led to a delayed phase inversion, thus hindering PEGMA segments in PVDF-g-PEGMA from migrating to the membrane surface. However, more residual PEGMA contributed to helping more PEGMA segments migrate to the membrane surface. The pure water fluxes of the blended membrane with reaction times of 9 h, 19 h, and 29 h are 5445 L·m⁻²·h⁻¹, 1068 L·m⁻²·h⁻¹and 1179 L·m⁻²·h⁻¹, respectively, at 0.07 MPa. Delayed phase inversion can form smaller surface pore size distributions, thus decreasing the water flux for the membranes with PVDF-g-PEGMA at 19 h and 29 h. Therefore, we can control the membrane pore size distribution by decreasing the reaction time of PVDF-g-PEGMA to obtain a better flux performance. The membrane with PVDF-g-PEGMA at 19 h exhibits the best foulant rejection and cleaning recovery due to its narrow pore size distribution and high surface oxygen content.     

The influence of mass transfer on solute transport in column experiments with an aggregated soil

The spreading of concentration fronts in dynamic column experiments conducted with a porous, aggregated soil is analyzed by means of a previously documented transport model (DFPSDM) that accounts for longitudinal dispersion, external mass transfer in the boundary layer surrounding the aggregate particles, and diffusion in the intra-aggregate pores. The data are drawn from a previous report on the transport of tritiated water, chloride, and calcium ion in a column filled with Ione soil having an average aggregate particle diameter of 0.34 cm, at pore water velocities from 3 to 143 cm/h. The parameters for dispersion, external mass transfer, and internal diffusion were predicted for the experimental conditions by means of generalized correlations, independent of the column data. The predicted degree of solute front-spreading agreed well with the experimental observations. Consistent with the aggregate porosity of 45%, the tortuosity factor for internal pore diffusion was approximately equal to 2. Quantitative criteria for the spreading influence of the three mechanisms are evaluated with respect to the column data. Hydrodynamic dispersion is thought to have governed the front shape in the experiments at low velocity, and internal pore diffusion is believed to have dominated at high velocity; the external mass transfer resistance played a minor role under all conditions. A transport model such as DFPSDM is useful for interpreting column data with regard to the mechanisms controlling concentration front dynamics, but care must be exercised to avoid confounding the effects of the relevant processes.     

Perceived and measured levels of environmental pollution: interdisciplinary research in the subarctic lowlands of northeast European Russia

Using interdisciplinary field research in the Usa Basin, northeast European Russia, we compared local inhabitants' perception of environmental problems with chemical and remote-sensing signatures of environmental pollution and their local impacts. Extensive coal mining since the 1930s around Inta and Vorkuta has left a legacy of pollution, detected by measuring snowpack, topsoil, and lichen chemistry, together with remote-sensing techniques and analysis of lake water and sediments. Vorkuta and its environs suffered the worst impacts, with significant metal loading and alkalization in lakes and topsoils, elevated metals and cations in terricolous (reindeer) lichens, and changes in vegetation communities. Although the coal industry has declined recently, the area boasts a booming oil and gas industry, based around Usinsk. Local perceptions and concerns of environmental pollution and protection were higher in Usinsk, as a result of increased awareness after a major oil spill in 1994, compared with Vorkuta's inhabitants, who perceived air pollution as the primary environmental threat. Our studies indicate that the principal sources of atmospheric emissions and local deposition within 25 to 40 km of Vorkuta were coal combustion from power and heating plants, coal mines, and a cement factory. Local people evaluated air pollution from direct observations and personal experiences, such as discoloration of snow and respiratory problems, whereas scientific knowledge played a minor role in shaping these perceptions.     

Modeling of indoor air treatment of polychlorinated dibenzo-p-dioxins and dibenzofurans using high-efficiency particulate air-carbon filtration

A high-efficiency particulate air (HEPA)-carbon filtration system was developed by the Access Business Group, LLC, to reduce the indoor levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The HEPA filter removes the particle-bound PCDD/Fs, and the carbon filter removes the gaseous fraction. Because of the toxicity of PCDD/Fs, it is very difficult to handle them in the laboratory. In this study, mathematical modeling was performed to evaluate the performance of the HEPA-carbon filtration system for PCDD/Fs removal and to optimize its design and operation. The model was calibrated with experimental data conducted with toluene in a sealed room. Model simulations with four selected congeners demonstrated that it takes approximately 1 hr for the indoor air treatment system to reach the maximum removal efficiency and that the carbon air filter has a life time of 10(7) yr for dioxin removal. Given a zero emission from the HEPA filter, the overall removal efficiency is 78.7% for 2,3,7,8-tetrachloro dibenzo-p-dioxins, 89.8% for octa-chlorodibenzodioxin, 78% for tetra-chlorodibenzofuran, and 89.8% for octa-chlorodibenzofuran. The larger the mass emission from the HEPA filter, the lower the overall removal efficiency, and the larger the ratio of the filter flow rate (Q(f)) to the room flow rate (Q), the higher the overall removal efficiency. When the ratio of Q(f)/Q is 15, an overall removal efficiency of 90% can be reached for all four of the selected compounds. The removal of the four selected compounds does not change as the relative humidity increases < or = 90%.     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.