Nitrification of an industrial wastewater in a moving-bed biofilm reactor: effect of salt concentration.

Nitrification of wastewaters from chemical industries can pose some challenges due to the presence of inhibitory compounds. Some wastewaters, besides their organic complexity present variable levels of salt concentration. In order to investigate the effect of salt (NaCl) content on the nitrification of a conventional biologically treated industrial wastewater, a bench scale moving-bed biofilm reactor was operated on a sequencing batch mode. The wastewater presenting a chloride content of 0.05 g l(-1) was supplemented with NaCl up to 12 g Cl(-) l(-1). The reactor operation cycle was: filling (5 min), aeration (12 or 24h), settling (5 min) and drawing (5 min). Each experimental run was conducted for 3 to 6 months to address problems related to the inherent wastewater variability and process stabilization. A PLC system assured automatic operation and control of the pertinent process variables. Data obtained from selected batch experiments were adjusted by a kinetic model, which considered ammonia, nitrite and nitrate variations. The average performance results indicated that nitrification efficiency was not influenced by chloride content in the range of 0.05 to 6 g Cl(-) l(-1) and remained around 90%. When the chloride content was 12 g Cl(-) l(-1), a significant drop in the nitrification efficiency was observed, even operating with a reaction period of 24 h. Also, a negative effect of the wastewater organic matter content on nitrification efficiency was observed, which was probably caused by growth of heterotrophs in detriment of autotrophs and nitrification inhibition by residual chemicals.

Is hydraulic retention time an essential parameter for MBR performance?

The effect of hydraulic retention time (HRT) on membrane bioreactors (MBR) operation is discussed. A brief literature review on this topic indicates that biased conclusions can be drawn if data is obtained under non steady-state conditions. Another relevant aspect regarding steady-state operation includes activated sludge adaptation to bioreactor running conditions. In addition, wastewater components also have influence on steady-state achievement and MBR performance.

Treatment of an industrial stream containing vinylcyclohexene by the H2O2/UV process.

Petrochemical industries generate wastewaters containing pollutants that can severely impact the biological treatment systems. Some streams from specific production units may contain nonbiodegradable or toxic compounds that impair the performance of the wastewater treatment plant and should be segregated and treated by specific techniques. In this work, the utilization of chemical oxidation (H2O2/UV) was investigated for removing 4-vinylcyclohexene (VCH) from a liquid stream coming from the production of hydroxylated liquid polybutadiene (HLPB). Besides VCH, this stream also contains ethanol, hydrogen peroxide, and many other organic compounds. Experiments were carried out in a small-scale photochemical reactor (0.7 L) using a 25-W low-pressure mercury vapor lamp. The photochemical reactor was operated in batch, and the reaction times were comprised between 10 and 60 min. Assays were also performed with a synthetic medium containing VCH, H2O2, and ethanol to investigate the removal of these substances in a less complex aqueous matrix. By-products formed in the reaction were identified by gas chromatography and mass spectroscopy (GC-MS). VCH was significantly removed by the oxidation process, in most assays to undetectable levels. Ethanol removal varied from 16 to 23 % depending on the reaction conditions. Acetic acid, acetaldehyde, and diols were detected as by-products of the industrial wastewater stream oxidation. A drop on the toxicity of the industrial stream was also observed in assays using the organism Artemia salina.

Removal of recalcitrant organic matter content in wastewater by means of AOPs aiming industrial water reuse.

This paper comes out from the need to provide an improvement in the current oil refinery wastewater treatment plant (WWTP) aiming to generate water for reuse. The wastewater was pretreated and collected in the WWTP after the biological treatment unit (bio-disks) followed by sand filtration. Ozonation (ozone concentration from 3.0-60 mgO3 L-1), UV (power lamp from 15 to 95 W), H2O2 (carbon:H2O2 molar ratio of 1:1, 1:2, and 1:4), and two advanced oxidation processes (UV/O3 and UV/H2O2) were investigated aiming to reduce the wastewater organic matter and generate water with suitable characteristics for the reverse osmosis operation and subsequent industrial reuse. Even after the biological and filtration treatments, the oil refinery wastewater still presented an appreciable amount of recalcitrant organic matter (TOC of 12-19 mgC L-1) and silt density index (SDI) higher than 4, which is considered high for subsequent reverse osmosis due to membrane fouling risks. Experiments using non combined processes (O3, H2O2, and UV only) showed a low degree of mineralization after 60 min of reaction, although the pretreatment with ozone had promoted the oxidation of aromatic compounds originally found in the real matrix, which suggests the formation of recalcitrant compounds. When the combined processes were applied, a considerable increase in the TOC removal was observed (max of 95 % for UV/O3 process, 55 W, 60 mgO3 L-1), likely due the presence of higher amounts of reactive species, specially hydroxyl radicals, confirming the important role of these species on the photochemical degradation of the wastewater compounds. A zero-order kinetic model was fitted to the experimental data and the rate constant values (k, mgC L-1 h-1) ranged from 4.8 < k UV/O3 < 11 ([O3]0 = 30-60 mg L-1), and 8.6 < k UV/H2O2 < 11 (C:H2O2 from 1:1 to 1:4). The minimum and maximum electrical energy per order (E EO) required for 60 min of treatment were calculated as 5.4 and 81 Wh L-1, respectively, for UV/O3 (15 W, 60 mgO3 L-1) and UV/H2O2 (95 W, 1C:1H2O2). Good results in terms of water conditioning for reverse osmosis operation were obtained using UV/H2O2 process with initial molar ratio of 1 C:2 H2O2 (UV lamp 55 W) and 1 C:4 H2O2 (UV lamp 95 W), and total organic carbon (TOC) removals of 62 % (SDI15 = 1.8) and 74 % (SDI15 = 2.0) were achieved, respectively, after 60 min. The treated wastewater followed to the reverse osmosis system, which operated with an adequate flux of permeate, was very efficient to remove salt and generate a permeate water with the required quality for industrial reuse.

Lipase production by solid-state fermentation: cultivation conditions and operation of tray and packed-bed bioreactors.

The production of lipase by Penicillium simplicissimum in solid-state fermentation was studied using babassu cake as the basal medium. Tray-type and packed-bed bioreactors were employed. In the former, the influence of temperature; content of the medium, and medium supplementation with olive oil, sugarcane molasses, corn steep liquor, and yeast hydrolysate was studied. For all combinations of supplements, a temperature of 30 degrees C, a moisture content of 70%, and a concentration of carbon source of 6.25% (m/m, dry basis) provided optimum conditions for lipase production. When used as single supplements olive oil and molasses also were able to provide high lipase activities (20 U/g). Using packed-bed bioreactors and molasses-supplemented medium, optimum conditions for enzyme production were air superficial velocities above 55 cm/min and temperatures below 28 degrees C. The lower temperature optimum found for these reactors is probably related to radial heat gradient formation inside the packed bed. Maximum lipase activities obtained in these bioreactors (26.4 U/g) were 30% higher than in tray-type reactors.

Process development for production of medium chain triglycerides using immobilized lipase in a solvent-free system.

The synthesis of tricaprylin, tricaprin, trilaurin, and trimyristin in a solvent-free system was conducted by mixing a commercial immobilized lipase with the organic reagents (glycerol and fatty acid) in a 20-mL batch reactor with constant stirring. The effects of temperature, fatty acid/glycerol molar ratio, and enzyme concentration on the reaction conversion were determined. The reactions were carried out for 26 h and the nonpolar phase was analyzed by gas chromatography. Appreciable levels of medium chain triglycerides were achieved, except for tricaprylin. The higher selectivity values for the production of triglycerides were attained under the following conditions: a fatty acid/glycerol molar ratio of 5; enzyme concentration of 5 or 9% (w/w); and temperatures of 70 degrees C (tricaprin), 80 degrees C (trilaurin), and 90 degrees C (trimyristin). After completion of the esterification reaction under these conditions, the recovery of the triglyceride and fatty acids, and the reusability of the enzyme were studied. The unreacted fatty acid and the produced triglyceride were satisfactorily recovered. The commercial immobilized lipase was used in 10 consecutive batch reactions at 80 degrees C, with 100% selectivity in the trilaurin and trimyristin synthesis. The possibility of enzyme reuse and the recovery of residual fatty acid are relevant results that contribute to increasing the viability of the process.

Enzymatic synthesis of medium chain monoglycerides in a solvent-free system.

The synthesis of monocaprin, monolaurin, and monomyristin in a solvent-free system was conducted by mixing a commercial immobilized lipase with the organic reactants (glycerol and fatty acids) in a 20-mL batch reactor with constant stirring. The effects of temperature, fatty acid/glycerol molar ratio, and enzyme concentration on the reaction conversion were determined. The addition of molecular sieves in the assays of monomyristin synthesis was also evaluated. The reactions were carried out for 5 to 6 h and the nonpolar phase was analyzed by gas chromatography. The best results in terms of selectivity and conversion (defined as the percentage of fatty acid consumed) were achieved when the stoichiometric amount of reagents (molar ratio = 1) and 9% (w/w) commercial enzyme were used and the reaction was performed at 60 degrees C. The addition of molecular sieves did not improve the synthesis of monomyristin. Conversions as high as 80%, with monoglycerides being the major products, were attained. After 5 h of reaction, the concentration of monoglyceride was about twice that of diglyceride, and only trace amounts of triglyceride were found. The results illustrate the technical possibility of producing medium chain monoglycerides in a solvent-free medium using a simple batch reactor.

Nitrification of industrial and domestic saline wastewaters in moving bed biofilm reactor and sequencing batch reactor.

Nitrification of saline wastewaters was investigated in bench-scale moving-bed biofilm reactors (MBBR). Wastewater from a chemical industry and domestic sewage, both treated by the activated sludge process, were fed to moving-bed reactors. The industrial wastewater contained 8000 mg Cl(-)/L and the salinity of the treated sewage was gradually increased until that level. Residual substances present in the treated industrial wastewater had a strong inhibitory effect on the nitrification process. Assays to determine inhibitory effects were performed with the industrial wastewater, which was submitted to ozonation and carbon adsorption pretreatments. The latter treatment was effective for dissolved organic carbon (DOC) removal and improved nitrification efficiency. Nitrification percentage of the treated domestic sewage was higher than 90% for all tested chloride concentrations up to 8000 mg/L. Results obtained in a sequencing batch reactor (SBR) were consistent with those attained in the MBBR systems, allowing tertiary nitrification and providing adequate conditions for adaptation of nitrifying microorganisms even under stressing and inhibitory conditions.

Ozonation of azo dyes (Orange II and Acid Red 27) in saline media.

Ozonation of two azo dyes was investigated in a monitored bench scale bubble column reactor (8.5-L), varying liquid media salt content (0, 1, 40 and 100 g L(-1), NaCl). In experiments with Orange II pH was varied (5, 7.5 and 9) but ozonation of Acid Red 27 was performed at pH 7.5. Ozone self-decomposition rate-constant increased with salt concentration. Color removal was very effective and fast achieved under all experimental conditions. For the two azo dyes tested, more than 98% of color intensity was removed in 30-min ozonation assays. However, only partial mineralization of azo dyes (45%-Orange II; 20%-Acid Red 27) was attained in such experiments. The degree of mineralization (TOC removal) was negatively affected by salt concentration. Biodegradation assays conducted by respirometry revealed the inhibitory effect of dye degradation products formed during ozonation.

Remediation of sandy soils using surfactant solutions and foams.

Remediation of sandy soils contaminated with diesel oil was investigated in bench-scale experiments. Surfactant solution, regular foams and colloidal gas aphrons were used as remediation fluids. An experimental design technique was used to investigate the effect of relevant process variables on remediation efficiency. Soils prepared with different average particle sizes (0.04-0.12 cm) and contaminated with different diesel oil contents (40-80 g/kg) were used in experiments conducted with remediation fluids. A mathematical model was proposed allowing for the determination of oil removal rate-constant (k(v)) and oil content remaining in the soil after remediation (C(of)) as well as estimation of the percentage of oil removed. Oil removal efficiencies obtained under the central experimental design conditions were 96%, 88% and 35% for aphrons, regular foams and surfactant solutions, respectively. High removal efficiencies were obtained using regular foams and aphrons, demanding small amounts of surfactant.

Production and regulation of lipase activity from Penicillium restrictum in submerged and solid-state fermentations.

Different carbon (C) sources, mainly carbohydrates and lipids, have been screened for their capacity to support growth and lipase production by Penicillium restrictum in submerged fermentation (SmF) and in solid-state fermentation (SSF). Completely different physiological behaviors were observed after the addition of easily (oleic acid and glucose) and complex (olive oil and starch) assimilable C sources to the liquid and solid media. Maximal lipolytic activities (12.1 U/mL and 17.4 U/g) by P. restrictum were obtained with olive oil in SmF and in SSF, respectively. Biomass levels in SmF (12.2-14.1 mg/mL) and SSF (7.0-8.0 mg/g) did not varied greatly with the distinct C sources used. High lipase production (12.3 U/g) using glucose was only attained in SSF, perhaps due to the ability of this fermentation process to minimize catabolite repression.