Development of Anaerobic High-Rate Reactors, Focusing on Sludge Bed Technology.

In the last 40 years, anaerobic sludge bed reactor technology has evolved from localized laboratory-scale trials to worldwide successful implementations in a variety of industries. High-rate sludge bed reactors are characterized by a very small footprint and high applicable volumetric loading rates. Best performances are obtained when the sludge bed consists of highly active and well settleable granular sludge. Sludge granulation provides a rich microbial diversity, high biomass concentration, high solids retention time, good settling characteristics, reduction in both operation costs and reactor volume, and high tolerance to inhibitors and temperature changes. However, sludge granulation cannot be guaranteed on every type of industrial wastewater. Especially in the last two decades, various types of high-rate anaerobic reactor configurations have been developed that are less dependent on the presence of granular sludge, and many of them are currently successfully used for the treatment of various kinds of industrial wastewaters worldwide. This study discusses the evolution of anaerobic sludge bed technology for the treatment of industrial wastewaters in the last four decades, focusing on granular sludge bed systems.

Thermal modification of activated carbon surface chemistry improves its capacity as redox mediator for azo dye reduction.

The surface chemistry of a commercial AC (AC(0)) was selectively modified, without changing significantly its textural properties, by chemical oxidation with HNO(3) (AC(HNO3)) and O(2) (AC(O2)), and thermal treatments under H(2) (AC(H2)) or N(2) (AC(N2)) flow. The effect of modified AC on anaerobic chemical dye reduction was assayed with sulphide at different pH values 5, 7 and 9. Four dyes were tested: Acid Orange 7, Reactive Red 2, Mordant Yellow 10 and Direct Blue 71. Batch experiments with low amounts of AC (0.1 g L(-1)) demonstrated an increase of the first-order reduction rate constants, up to 9-fold, as compared with assays without AC. Optimum rates were obtained at pH 5 except for MY10, higher at pH 7. In general, rates increased with increasing the pH of point zero charge (pH(pzc)), following the trend AC(HNO3) < AC(O2) < AC(0) < AC(N2) < AC(H2). The highest reduction rate was obtained for MY10 with AC(H2) at pH 7, which corresponded to the double, as compared with non-modified AC. In a biological system using granular biomass, AC(H2) also duplicated and increase 4.5-fold the decolourisation rates of MY10 and RR2, respectively. In this last experiment, reaction rate was independent of AC concentration in the tested range 0.1-0.6 g L(-1).

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes.

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.

Sulfide removal by moderate oxygenation of anaerobic sludge environments.

Introduction of a limited amount of oxygen to anaerobic bioreactors is proposed as a simple technique to lower the level of sulfide in the biogas. This paper presents the results of a bioreactor study and of batch experiments that were performed to obtain better insight into the fate of sulfur compounds and oxygen during micro-aerobic sulfide oxidation. Introduction of a low airflow (0.7-0.9 m(3)m(-3)d(-1), corresponding to an O(2)/S molar ratio of 8-10) to a fluidized bed reactor fed with low-sulfate vinasse was sufficient to reduce the biogas H(2)S-content to an undetectable level. Sulfide was initially oxidized to elemental sulfur, thiosulfate and - most probably - polysulfide. Significant sulfate production did not occur. Bioreactor sludge sampled from the reactor after three weeks' micro-aerobic operation was much faster in oxidizing sulfur than bioreactor sludge sampled during fully anaerobic reactor operation. The reaction proceeded faster with increasing O(2)/sulfide ratios.

Automated equipment for anaerobic sludge parameters determination.

Methanogenic activity, anaerobic biodegradability and toxicity are key parameters in the design and operation of anaerobic bioreactors. A large variety of methods exist for the determination of these parameters but a normalized method has not been established so far. This paper presents the development of an automated manometric system for the determination of these anaerobic sludge parameters. The system is based on monitoring the production of methane by using a pressure transducer that measures the pressure in a gas-collecting chamber of known adjustable volume, which is independent of the space where biogas production takes place. The evolution of pressure generated by the accumulation of methane relates to the conversion of COD. In this way, the methanogenic activity of the sludge can be determined, as well as the biodegradability of solids and liquid, as well as the methanogenic toxicity of compounds. The equipment permits gas sampling, as well as extraction and introduction of liquid, without losing the anaerobic conditions. Various assays have been conducted to test the reliability and reproducibility of the obtained results, showing a high level of both. The methanogenic activities obtained in the assays ranged between 0.1 and 1.8 g COD g(-1) VSS d(-1), and the biodegradability of the organic compounds tested ranged between 20 and 90%.

Advances in high-rate anaerobic treatment: staging of reactor systems.

Anaerobic wastewater treatment (AnWT) is considered as the most cost-effective solution for organically polluted industrial waste streams. Particularly the development of high-rate systems, in which hydraulic retention times are uncoupled from solids retention times, has led to a world-wide acceptance of AnWT. In the last decade up to the present, the application potentials of AnWT are further explored. Research shows the feasibility of anaerobic reactors under extreme conditions, such as low and high temperatures. Also toxic and/or recalcitrant wastewaters, that were previously believed not to be suitable for anaerobic processes, are now effectively treated. The recent advances are made possible by adapting the conventional anaerobic high-rate concept to the more extreme conditions. Staged anaerobic reactor concepts show advantages under non-optimal temperature conditions as well as during the treatment of chemical wastewater. In other situations, a staged anaerobic-aerobic approach is required for biodegradation of specific pollutants, e.g. the removal of dyes from textile processing wastewaters. The current paper illustrates the benefits of reactor staging and the yet un-exploited potentials of high-rate AnWT.

Application of redox mediators to accelerate the transformation of reactive azo dyes in anaerobic bioreactors.

Azo dyes are nonspecifically reduced under anaerobic conditions but the slow rates at which reactive azo dyes are converted presents a serious problem for the application of anaerobic technology as a first stage in the complete biodegradation of these compounds. As quinones have been found to catalyze reductive transfers by acting as redox mediators, the application of anthraquinone-2,6-disulfonic acid (AQDS) during continuous anaerobic treatment of the reactive azo dye, Reactive Red 2 (RR2), was evaluated. A mixture of volatile fatty acids was used as the electron-donating primary substrate. Batch experiments demonstrated that AQDS could increase the first-order rate constant of RR2 reductive cleavage by one order of magnitude. In the continuous experiment, treatment of RR2 containing synthetic wastewater in a lab-scale upflow anaerobic sludge blanket (UASB) reactor yielded low dye removal efficiencies (<30%). Consequently, severe toxicity problems occurred, eventually resulting in almost complete inhibition of the methanogenic activity. Addition of catalytic concentrations of AQDS (19 microM) to the reactor influent caused an immediate increase in the dye removal efficiency and recovery of biological activity. Ultimately, RR2 removal efficiency stabilized at 88%, and higher AQDS loads resulted in higher RR2 removal efficiencies (up to 98% at 155 microM AQDS). Examination of the RR2 decolorizing properties of dye-adapted reactor sludge and of nonadapted reactor seed sludge revealed that RR2 decolorization was principally a biologically driven transfer of reducing equivalents from endogenous and added substrates to the dye. Hydrogen, added in bulk, was clearly the preferred electron donor. Bacteria that couple dye decolorization to hydrogen oxidation were naturally present in seed sludge. However, enrichment was required for the utilization of electrons from volatile fatty acids for dye reduction. The stimulatory effect of AQDS on RR2 decolorization by AQDS-unadapted sludge was mainly due to assisting the electron transfer from endogenous substrates in the sludge to the dye. The stimulatory effect of AQDS on RR2 decolorization by sludge from the AQDS-exposed reactor was, in addition, strongly associated with the transfer of electrons from hydrogen and acetate to the dye, probably due to enrichment of specialized AQDS-reducing bacteria.

Enhanced decolourisation of acid orange 7 in a continuous UASB reactor with quinones as redox mediators.

The reductive biotransformation of acid orange 7 (AO7) was explored in a lab-scale upflow anaerobic sludge blanket (UASB) reactor at low hydraulic residence times (HRT). A colour removal of 85% was achieved when the reactor was operated at a HRT of 6 hours, but decreased up to 70% when the HRT was lowered to 2 hours. Addition of the quinone model compound, anthraquinone 2,6-disulfonate (AQDS), as redox mediator, allowed for a considerably higher decolourising efficiency (> 90% at all the HRT evaluated). The results indicate that the use of catalytic concentrations of AQDS (AQDS/AO7 molar ratio about 0.01) can accelerate decolourising processes achieving satisfying extent of decolourisation.

Azo dye decolourisation by anaerobic granular sludge.

The decolourisation of 20 selected azo dyes by granular sludge from an upward-flow anaerobic sludge bed (UASB) reactor was assayed. Complete reduction was found for all azo dyes tested, generally yielding colourless products. The reactions followed first-order kinetics and reaction rates varied greatly between dyes: half-life times ranged from 1 to about 100 h. The slowest reaction rates were found for reactive dyes with a triazine reactive group. There was no correlation between a dye's half-life time and its molecular weight, indicating that cell penetration was probably not an important factor. Since granular sludge contains sulphide, eight dyes were also monitored for direct chemical decolourisation by sulphide. All these dyes were reduced chemically albeit at slower rates than in the presence of sludge at comparable sulphide levels. Increasing sulphide concentrations, even when present in huge excess, stimulated the azo reduction rate. The results indicate that granular sludge can decolourise a broad spectrum of azo dye structures due to non-specific extracellular reactions. Reducing agents (e.g., sulphide) in sludge play an important role. The presence of anaerobic biomass is probably beneficial for maintaining the pools of these reduced compounds.