Well-dispersed titanium dioxide and silver nanoparticles on external and internal surfaces of asymmetric alumina hollow fibers for enhanced chromium (VI) photoreductions.

Heterogenous photocatalysis is a suitable alternative for wastewater treatment. The supporting of the solid catalyst in a porous material is suggested to facilitate catalyst recovery and reuse. Here we propose for the first time the evaluation of supporting silver (Ag)-decorated titanium dioxide (TiO2) catalysts on internal and external surfaces of alumina hollow fibers with asymmetric pore size distribution. The produced catalysts were considered for Cr(VI) photoreductions. The ultrasound-assisted process potentialized the distribution of Ag nanoparticles on the TiO2 surface. The loading of Ag nanoparticles at concentrations greater than 5 wt% was necessary to improve the TiO2 activity for Cr(VI) photoreduction. The loading of Ag nanoparticles at 30 wt% improved the Cr(VI) photoreduction of the single TiO2 catalyst from 40.49 ± 0.98 to 55.00 ± 0.83% after 180 min of reaction. Suspended and supported Ag-decorated TiO2 catalysts achieved total Cr(VI) photoreduction after 21 h of reaction. The adjusted reaction rate constant with the externally supported Ag-TiO2 catalyst was 3.57 × 10-3 ± 0.18 × 10-3 min-1. Similar reaction rate constants were achieved with suspended and internally supported catalysts (approximately 2.70 × 10-3 min-1). After 10 sequential reuses, all catalysts presented similar Cr(VI) photoreductions of approximately 66%. Nevertheless, the use of the externally supported catalyst is suggested for Cr(VI) photoreductions due to its superior catalyst activity at least in the first reuse cycles.

Slow release fertilizer prepared with lignin and poly(vinyl acetate) bioblend.

Controlled or slow release fertilizers have been recommended to enhance crop yield, while minimizing environmental and economic issues related from current fertilizer applications. However, alternative biodegradable and non-toxic coating material should be suggested to produce biocoated fertilizers. Here we propose the use of lignin and poly(vinyl acetate) (PVAc) as biocoating materials for preparing slow release urea fertilizer. The blend of PVAc and lignin at a mass ratio of 75:25 improved the characteristics of the formed film and increased the nitrogen release time if compared to the pure polymers. The nitrogen release time from urea granules coated with a polymeric layer of 154.3 ±â€¯5.5 µm formed by lignin and PVAc was 36 times greater than from bare urea. The increase in the polymeric coating from 52.6 ±â€¯5.2 to 80.2 ±â€¯6.1 µm decreased the curvature of the nitrogen release data by a factor of at least 1.7, while the curvature was decreased in at least 1.3 with the increase in the polymeric coating from 80.2 ±â€¯6.1 to 158.9 ±â€¯10.6 µm. The adjustment of nitrogen release data to the Peppas-Sahlin model indicated the Fickian diffusion is more predominant than relaxation contributions, since the used polymers did not present considerable swelling. Thus, the blending of PVAc and lignin at 25 wt% of lignin and 75 wt% of PVAc is suggested as a biocoating material for producing slow release fertilizers.

Forward Black Liquor Acid Precipitation: Lignin Fractionation by Ultrafiltration.

Lignin recovery from black liquor is an important task for producing valuable chemical products. Acidification processes are currently applied by pulp and paper industries for black liquor treatment, in which two main streams are produced: the precipitated lignin fraction and a lignin-lean black liquor. Membrane filtration is a suitable alternative for lignin recovery from black liquor, but studies on lignin-lean black liquor filtration are scarce. Here, we evaluated the ultrafiltration process for lignin recovery from the both fractions of black liquor acidification. The lignin-lean black liquor presented 22 wt% of total solids with 4.6 wt% of lignin. Lignin retention from the lignin-lean black liquor by the 5 kDa ultrafiltration membrane was equal to 85%, with reduction in total solid concentration from 219.8 to 68.1 g L-1. Due to the relatively high solid concentration in the lignin-lean black liquor, cake formation was the main fouling mechanism during ultrafiltrations. The precipitated lignin solution presented 4.8 wt% of total solids with equivalent lignin concentration (4.7 wt%). The used membrane was able to retain almost 100% of solids and lignin from the solution prepared from the precipitated lignin. All fouling mechanisms were responsible for flux decay in ultrafiltration of the precipitated lignin solution. Steady state fluxes for lignin-lean black liquor and precipitated lignin solution were 0.9 and 15.9 L h-1 m-2, respectively. According to TGA analyses up to 800 °C, precipitated lignin and lignin-lean black liquor presented total mass losses of 63.5% and 44.3%, respectively. Also, the permeate samples presented lower mass losses than their respective feed samples. The ultrafiltration process reduced the average weight molar mass (Mw) of the precipitated lignin solution and lignin-lean black liquor from 1817 to 486 g mol-1and from 2876 to 1095 g mol-1, respectively. Thus, the 5 kDa ultrafiltration membrane was efficient for lignin recovery from the lignin-lean black liquor, while membranes with lower cut-off should be proposed for lignin purification from the precipitated fraction.

Photoreduction of chromium(VI) in microstructured ceramic hollow fibers impregnated with titanium dioxide and coated with green algae Chlorella vulgaris.

Here we propose an innovative photocatalytic hybrid system for the reduction of hexavalent chromium (Cr(VI)) from aqueous solutions. The hybrid system was composed of titanium dioxide (TiO2) immobilized in the micro-voids of asymmetric alumina hollow fibers and of the green algae Chlorella vulgaris coated on the outer sponge-like layer of the fiber. The photoreduction of Cr(VI) was systematically studied in different systems: single systems with TiO2 or algae; the synergistic system of algae combined with TiO2; and the proposed hybrid system composed of TiO2 and algae supported in ceramic hollow fibers. Morphological and energy dispersive spectroscopy analyses showed that TiO2 and the algae were properly supported in the substrate (alumina hollow fibers). For an initial Cr(VI) concentration of 10 mg L-1 and dosages of 1 g L-1 of TiO2 and algae, the hybrid system resulted in total Cr(VI) reduction after 16 h of process. Additionally, the efficiency of the hybrid system for Cr(VI) reduction was reduced in only 9% after 5 cycles of reuse and in 42% after 10 cycles of reuse. Thus, micro-structured ceramic hollow fibers impregnated with TiO2 and decorated with the green algae C. vulgaris was efficient for Cr(VI) reductions.