Influence of Nitrate and Sulfate on the Anaerobic Treatment of Pharmaceutical Wastewater

Anaerobic treatment of wastewater from the pharmaceutical industry, which contained about 3.2 g/L of sulfate, was carried out in an Upflow Anaerobic Sludge Blanket (UASB) reactor. After a startup period of 120 days, a chemical oxygen demand (COD) removal efficiency of more than 90 % was obtained along with an organic loading rate (OLR) of 1.5 g COD/(L day). During the same period, the sulfate removal was about 90 %. However, the performance of the reactor was affected when the loading rate was increased to 2.09 g COD/(L day). It was found that the accumulation of sulfides, combined with a decrease in the pH, affected the reactor performance. In batch reactor studies with pharmaceutical wastewater it was observed that methane production began only after the initiation of nitrate consumption. The denitrification process can inhibit sulfate reduction at high nitrate concentrations, but compared to reactors without nitrate, the sulfate reduction process and sulfide formation were quickly initiated at low nitrate concentrations. The methanogenic activity was however affected by the presence of more than 2 g/L of sulfate.     

Study of the Operability of a Continuous Bioreactor for the Pre‐fermentation of Cheese Culture

The dynamics of a continuous stirred‐tank bioreactor for cheese pre‐fermentation is analyzed using elementary concepts of bifurcation theory and continuation techniques. The bioreactor model, which was previously developed and validated, explicitly incorporates the effect of uncontrolled pH levels. The stability analysis of the model is carried out for two cases: In the first case, the bioreactor is equipped with a seed tank, while the second case involves no additional seed tank. The static analysis allows useful analytical results for the study of steady state multiplicity of the model to be derived. The results of this paper provide practical guidelines on the selection of operating parameters that can eliminate difficult operating regions and that can consequently improve the operability of the bioreactor.     

The Role of the Liquid Phase in the Degradation of Toluene and m‐Cresol within a Biofilm Trickle‐Bed Reactor

The degradation of toluene and m‐cresol in a biofilm trickle‐bed reactor was experimentally and theoretically investigated. Degradation is the result of the cooperation between suspended and immobilized microorganisms in the trickling film and the biofilm. The role of the trickling film is that of a barrier for mass transfer to the biofilm or that of an additional reaction space. This is the result of physical availability of pollutants to the liquid phase as well as co‐substrate degradation of inherent biomass. An instationary reactor balance model is presented. In addition to this the change in wetting behavior of carrier surface due to biofilm formation is discussed. A partial wetting of biofilm surface by rivulets of the trickling film is proposed. The model was verified by experimental data. The different reactor operation modes denoted as biofilm regime versus trickling film regime for the chosen pollutant system were expressed in terms of dimensionless reactions and transfer numbers. It is shown that the volumetric reaction rates for toluene in a trickling film regime reaches values twice as high as that of a biofilm regime due to the presence of the second substrate m‐cresol. The limiting step in both cases is the mass transfer of oxygen to bacteria in the biofilm or trickling film.     

The Rotary Trickle‐Bed Reactor – A New Reactor Concept for Biological Gas Purification

A new type of reactor employed to the biological gas purification is presented. The avoidance of clogging in the carrier packing is achieved by i) the use of a structured, rotating carrier packing, ii) a definite liquid irrigation regime during start‐up, operation and clean‐up time phases, iii) an on‐line determination and control of the fixed biofilm mass. A uniform biofilm thickness is generated by an optimized liquid irrigation of the carrier packing with spray nozzles. The detachment of the fixed biomass is accomplished by liquid shear forces generated with jet nozzles. The time‐scheduled operation regime of the reactor is founded on the on‐line quantification of the immobilized biomass, which results in a new quality of process governing of biotrickling reactors applied to gas purification. This is proved by the experimental results of pressure drop, dynamic liquid holdup as well as the volumetric degradation rates. The degradation of styrene was investigated in laboratory and field experiments showing a maximal volumetric degradation rate of 150 g m^–3 h^–1 at a pollutant load of 200 g m^–3 h^–1. The feasibility of this reactor prototype is demonstrated by employing it to the elimination of industrial waste gas.     

Kinetics of Veratryl Alcohol Oxidation by Lignin Peroxidase and in situ Generated Hydrogen Peroxide in an Electrochemical Reactor

The cathodic reduction of oxygen to hydrogen peroxide, the current efficiency for the production of H₂O₂ and the oxidation of veratryl alcohol with an in situ generated hydrogen peroxide‐lignin peroxidase complex were studied in this paper. The complex was prepared by utilizing a novel preparation technique in an electrochemical reactor. The oxidation of veratryl alcohol (VA; 3,4‐dimethoxybenzyl alcohol) was carried out with or without lignin peroxidase under an electric field. The redox properties of veratryl alcohol on a carbon electrode in the presence of lignin peroxidase have been investigated using cyclic voltammetry. The kinetics of veratryl alcohol oxidation in an electrochemical reactor were compared to the oxidation when hydrogen peroxide was supplied externally. Further, the oxidation of veratryl alcohol by lignin peroxidase was optimized in terms of enzyme dosage, pH, and electrical potential. The novel electroenzymatic method was found to be effective using in situ generated hydrogen peroxide for the oxidation of veratryl alcohol by lignin peroxidase.     

Characterization and properties of catalase immobilized onto controlled pore glass and its application in batch and plug-flow type reactors

Bovine liver catalase was covalently immobilized onto controlled pore glass (CPG) beads modified with 3-aminopropyltriethoxysilane (3-APTES) followed by treatment with glutaraldehyde. Coupling of catalase onto CPG was optimized to improve the efficiency of the overall immobilization procedure. The optimum coupling conditions: pore diameter of CPG, pH, buffer concentration, temperature, coupling time and initial catalase amount per grams of carrier were determined as 70 nm, 6.0, 75 mM, 5 °C, 7 h and 6 mg catalase, respectively. Catalytic efficiencies (k_cat/K_m) and thermal inactivation rate constants (k_i) of ICPG1 were determined and compared with that of free catalase. Suitability of ICPG1 was also investigated by using it in batch and plug-flow type reactors. When the remaining activity of ICPG1 retained was about 50% of its initial activity the highest total productivity of ICPG1 was determined as 7.6 × 10⁶ U g immobilized catalase⁻¹ in plug-flow type reactor. However, the highest total productivity of ICPG1 was 6.2 × 10⁵ U g immobilized catalase⁻¹ in batch type reactor. ICPG1 may have great potentials as biocatalyst for the application in decomposition of hydrogen peroxide in plug-flow type reactor.     

Bonding Form Analysis of Metals and Sulfur Fractionation in Methanol‐Grown Anaerobic Granular Sludge

This study investigates the metal and sulfur bonding form distribution in mesophilic (30 °C, pH 7) methanol‐grown anaerobic granular sludge from upflow anaerobic sludge bed reactors operating at an organic loading rate of 3.8 g CH₃OH‐COD/L d. This was achieved by applying a modified Tessier sequential extraction scheme to investigate the metal bonding forms and a sequential extraction scheme for sulfur and simultaneously extracted metals to granular sludge samples of the reactors after 0, 22, 35 and 43 days of operation. Metals were also determined in the sulfur extracts. Co and Ni predominated in their oxidizable bonding forms, which increased together with the pseudo‐total content during reactor operation. An omission of Co and Ni from the influent led to only a minor decline of the pseudo‐total content in the sludge, mainly from the acid‐soluble fraction. The ratio of simultaneously extracted metals (Co, Fe, Mn, Ni) to acid‐volatile sulfides was lower than 1, indicating that the sludge contained sufficient sulfide to bind the metals as metal monosulfides. The bioavailability of metals in the methanol‐grown anaerobic granular sludge investigated is therefore mainly controlled by sulfide formation/dissolution.     

Experimental Study of Mass Transfer Phenomena in a Cross Flow Membrane Bioreactor: Aeration and Membrane Separation

Experimental work carried out on wastewater from a wastewater treatment plant (WWTP) showed that in a cross flow membrane bioreactor the gas/liquid transfer is highly dependent on the biomass concentration. In new biological wastewater membrane treatment processes (mostly using deep end membranes), the biomass concentration is usually about 15 g/L, which entails a decrease in the bioreactor aeration capacity by a factor of approximately four compared with clean water. The gas/liquid transfer may therefore become a limiting step in this type of process. To prevent the operating costs of the biological treatment from increasing, it is imperative that the oxygen transfer be optimized. Membrane experiments showed that the permeate flux is highly dependent on the biomass concentration and the tangential velocity in the membrane module.     

Modeling of a Catalyzed Reaction Using Lipase Immobilized in a Poly(vinyl alcohol) Membrane

A mathematical model for the hydrolysis reaction of p‐nitro phenol laurate catalyzed by a lipase immobilized in a membrane was developed. In an earlier study this model reaction was found to show very different reaction rates when it was performed in aqueous micellar solution with free enzyme and with membrane immobilized enzyme. It was assumed that a local accumulation of substrate in the membrane is responsible for the observed rate enhancement. The conversion of p‐nitro phenol ester within the membrane was modeled by considering a combination of the convective flow through poly(vinyl alcohol) membrane pores, concentration polarization of substrate containing micelles at the membrane surface and the kinetics of the reaction with free enzymes. It was demonstrated that the model offered a comprehensive understanding of the interaction of the involved phenomena. The modeling results are in good agreement with the experimental data from 10 runs with different enzyme and substrate concentrations. The substrate concentration at the membrane surface increased by up to a factor of 3 compared to the feed concentration. This effect explains the observed rate enhancement. Moreover, the model was used to determine the unknown parameters, i.e., the intrinsic retention and the mass transfer coefficient, by fitting the model to the experimental data. The model may also be used to calculate the optimum operating conditions and design parameters of such a reactor.     

Biomass Pyrolysis in an Argon/Hydrogen Plasma Reactor

This paper presents the experimental results of biomass pyrolysis in a laboratory argon/hydrogen plasma reactor. The samples tested were wood and rice husk. The gaseous product was found to contain mainly H₂, CO, C₂H₂ and CH₄. The conversion of carbon and oxygen from the biomass feed to gaseous product can reach up to 79 % and 72 %, respectively. The results indicate that plasma pyrolysis of biomass may be a useful way for gaseous fuel production.