A novel membrane bioreactor for detoxifying industrial wastewater: II. Biodegradation of 3-chloronitrobenzene in an industrially produced wastewater

A novel membrane bioreactor has been used for the treatment of an industrially produced wastewater arising in the manufacture of 3-chloronitrobenzene. This wastewater is not amenable to direct biological treatment without some form pretreatment or dilution, due to the inorganic composition (pH <1, salt concentration 4% w/w) of the wastewater. In the membrane bioreactor, the organic pollutants are first separated from the wastewater by selective membrane permeation, and then biodegraded in the biological growth compartment of the bioreactor. At a wastewater flow rate of 64 mL h(-1) (corresponding to a contact time of approximately 1.7 hours) over 99% of the 3-chloronitrobenzene and over 99% of the nitrobenzene in the wastewater were degraded. Degradation of 3-chloronitrobenzene was accompanied by evolution of chloride ions in a stoichiometric ratio. Both 3-chloronitrobenzene and nitrobenzene degradation were accompanied by the evolution of carbon dioxide; approximately 80% of the carbon entering the system was oxidized to CO(2) carbon. Analysis of mass transport across the membrane revealed that 3-chloronitrobenzene and nitrobenzene are transported more rapidly than phenol. This is explained in terms of a resistances-in-series model, which shows phenol transfer to be rate limited by the membrane diffusion step, whereas the chloronitrobenzene and nitrobenzene transfer are rate limited by the liquid film mass transfer. (c) 1993 Wiley & Sons, Inc.     

Determination of pollutant diffusion coefficients in naturally formed biofilms using a single tube extractive membrane bioreactor

A novel technique has been used to determine the effective diffusion coefficients for 1,1,2-trichloroethane (TCE), a nonreacting tracer, in biofilms growing on the external surface of a silicone rubber membrane tube during degradation of 1,2-dichloroethane (DCE) by Xanthobacter autotrophicus GJ10 and monochlorobenzene (MCB) by Pseudomonas JS150. Experiments were carried out in a single tube extractive membrane bioreactor (STEMB), whose configuration makes it possible to measure the transmembrane flux of substrates. A video imaging technique (VIT) was employed for in situ biofilm thickness measurement and recording. Diffusion coefficients of TCE in the biofilms and TCE mass transfer coefficients in the liquid films adjacent to the biofilms were determined simultaneously using a resistances-in-series diffusion model. It was found that the flux and overall mass transfer coefficient of TCE decrease with increasing biofilm thickness, showing the importance of biofilm diffusion on the mass transfer process. Similar fluxes were observed for the nonreacting tracer (TCE) and the reactive substrates (MCB or DCE), suggesting that membrane-attached biofilm systems can be rate controlled primarily by substrate diffusion. The TCE diffusion coefficient in the JS150 biofilm appeared to be dependent on biofilm thickness, decreasing markedly for biofilm thicknesses of >1 mm. The values of the TCE diffusion coefficients in the JS150 biofilms <1-mm thick are approximately twice those in water and fall to around 30% of the water value for biofilms >1-mm thick. The TCE diffusion coefficients in the GJ10 biofilms were apparently constant at about the water value. The change in the diffusion coefficient for the JS150 biofilms is attributed to the influence of eddy diffusion and convective flow on transport in the thinner (<1-mm thick) biofilms.     

A membrane bioreactor for biotransformations of hydrophobic molecules

The Membrane Bioreactor for Biotransformations (MBB) is based on the aqueous/organic two-phase system, and uses a tubular silicone rubber membrane to separate the two liquid phases. This avoids the key problem associated with direct contact two-phase processes, specifically, product emulsification. The baker's yeast mediated reduction of geraniol to citronellol was used as a model biotransformation to demonstrate MBB operation. Values for the overall mass transfer coefficient were determined for geraniol, (2.0 x 10(-5) ms-1), and for citronellol, (2.1 x 10(-5) ms-1) diffusion across the silicone rubber membrane. Using these values, and the specific activity of the biocatalyst (5 nmols-1g biomass-1), a suitable membrane surface area: biomass ratio was determined as 2.4 x 10(-3) m2g biomass-1. The bioreactor was operated at this surface area: biomass ratio and achieved a product accumulation rate 90-95% that of a conventional direct contact two-phase system. The slight reduction in product accumulation rate was shown not to be due to mass transfer limitations with respect to reactant delivery or product extraction. Copyright 1998 John Wiley & Sons, Inc.     

Biodegradation of high phenol containing synthetic wastewater by an aerobic fixed bed reactor

The continuous aerobic degradation of phenol, mixed with readily degradable synthetic wastewater was studied over a period of 400 days at 25+/-5 degrees C temperature in a fixed bed biofilm reactor using 'Liapor' clay beads as packing material. The phenol concentration added to the reactor ranged from 0.19 to 5.17g/l and was achieved by a gradual increase of phenol in wastewater, thus adapting the microbial flora to high contaminant concentrations. A maximal removal rate of 2.92g phenol/(ld) at a hydraulic retention time (HRT) of 0.95 days and a total organic loading rate (OLR) of 15.3g COD/(ld) with a phenol concentration of 4.9g/l was observed. However, this was not a stable rate at such high phenol loading. At the end of reactor operation on day 405, the phenol removal rate was 2.3g/(ld) at a influent phenol concentration of 4.9g/l. There were no phenol intermediates present in the reactor, as evident from corresponding COD, phenol removal and the absence of fatty acids. Omission of organic nitrogen compounds or of urea in influent feed was not favourable for optimal phenol removal. The phenol degradation profile that was studied in shake flasks indicated that the presence of a acetate which represent as an intermediate of phenol degradation retarded the phenol degradation. The highest phenol degradation rate observed in batch assays was 3.54g/(ld).     

Nitrification using polyvinyl alcohol-immobilized nitrifying biofilm on an O2-enriching membrane

A combination of cell immobilization and membrane aeration approaches was used in a biological reactor to treat NH₄ ⁺ in wastewater. Nitrifying microorganisms, immobilized by polyvinyl-alcohol (PVA) and attached to the surface of a silicone membrane tube, were used to develop a novel reactor for nitrification. The immobilized biofilm had a rubber-like elasticity and resisted shear stress over 5 months of operation. The reactor removed 95% of ammonium, added at 1.97 g N m^–2 d^–1, with O_–2 enriching the membrane.     

Process development for degradation of phenol by Pseudomonas putida in hollow-fiber membrane bioreactors

The degradation of phenol (100-2800 mg/L) by cells Pseudomonas putida CCRC14365 in an extractive hollow-fiber membrane bioreactor (HFMBR) was studied, in which the polypropylene fibers were prewetted with ethanol. The effects of flow velocity, the concentrations of phenol, and the added dispersive agent tetrasodium pyrophosphate on phenol degradation and cell growth were examined. It was shown that about 10% of phenol was sorbed on the fibers at the beginning of the degradation process. The cells P. putida fully degraded 2000 mg/L of phenol within 73 h when the cells were immobilized and separated by the fibers. Even at a level of 2800 mg/L, phenol could be degraded more than 90% after 95-h operation. At low phenol levels (< 400 mg/L) where substrate inhibition was not severe, it was more advantageous to treat the solution in a suspended system. At higher phenol levels (> 1000 mg/L), however, such HFMBR-immobilized cells could degrade phenol to a tolerable concentration with weak substrate-inhibition effect, and the degradation that followed could be completed by suspended cultures due to their larger degradation rate. The process development in an HFMBR system was also discussed.     

Influence of recirculation on the performance of anaerobic sequencing batch biofilm reactor (AnSBBR) treating hypersaline composite chemical wastewater

Influence of recirculation on the performance of anaerobic sequencing batch biofilm reactor (AnSBBR) was studied in the process of treating hypersaline (total dissolved inorganic solids (TDIS) approximately 26 g/l) and low biodegradable (BOD/COD approximately 0.3) composite chemical wastewater. Significant enhancement in the substrate removal efficiency and biogas yield was observed after introducing the recirculation to the system. Maximum efficiency (COD removal efficiency - 51%; SDR - 3.14 kg COD/cum-day) was observed at recirculation to feed (R/F) ratio of 2 (OLR - 6.15 kg C OD/cum-day; HLR - 2.30 cum (liquid)/cum day; UFV(A) - 0.023 m/h). Subsequent increase of R/F to 3 (OLR - 6.15 kg COD/cum-day; HLR - 3.07cum (liquid)/cum-day; UFV(A) - 0.035 m/h) resulted in reduction in COD removal efficiency (32%; SDR - 1.97 kg COD/cum-day). The enhanced performance of the system due to the introduction of recirculation was attributed to the improvement in the mass transfer between the substrate present in the bulk liquid and the attached biofilm. The hydrodynamic behavior due to recirculation mode of operation reduced the concentration gradient (substrate inhibition) of substrate and reaction by-products (VFA) resulting in mixed flow conditions.     

Microbial fouling of reverse-osmosis membranes used in advanced wastewater treatment technology: chemical, bacteriological, and ultrastructural analyses.

Biofouling of reverse-osmosis membranes was investigated at an advanced wastewater treatment facility. Cellulose diacetate membranes operated for approximately 4,000 h became uniformly coated with a mucilaginous fouling layer. The fouling material was approximately 93% water by weight, and nearly 90% of the dehydrated residue was organic in composition. Calcium, phosphorous, sulfur, and chlorine were the major inorganic constituents detected. Protein and carbohydrate represented as much as 30 and 17%, respectively, of the dry weight of the biofilm. Bacteriological plate counts indicated up to 5.6 X 10(6) CFU/cm2 of membrane surface. Accumulation of [3H]glucose in the biofilm and measurement of ATP indicated that the fouling bacteria were metabolically active in situ. The genus Acinetobacter and the Flavobacterium-Moraxella group were the major generic groups associated with the feedwater surface of the membrane, whereas species of the generic groups Acinetobacter, Pseudomonas-Alcaligenes, and Bacillus-Lactobacillus predominated on the permeate water surface. Electron microscopy revealed that the biofilm on the feedwater surface of the membrane was 10 to 20 microns thick and was composed of several layers of compacted bacterial cells, many of which were partially or completely autolyzed. The bacteria were firmly attached to the membrane surface by an extensive network of extracellular polymeric fibrils. Polyester (Texlon) support fibers located on the permeate surface of the reverse osmosis membranes were sparsely colonized, suggesting bacterial regrowth in the product water collection system.     

Reductive dechlorination of 2-chlorophenol in a hydrogenotrophic, gas-permeable, silicone membrane bioreactor

A gas-permeable silicone membrane bioreactor was used to cultivate the biofilm under hydrogenotrophic condition for reductive dechlorination of 2-chlorophenol (2-CP). The anaerobic sludge obtained from a swine wastewater treatment plant was immobilized by polyvinyl alcohol (PVA) so as to form a biofilm on the surface of the silicone tube. After acclimating for about 4 months, the bioreactor showed a high dechlorinating performance. Under the condition of continuous feeding with 2-CP at 25 mg/l and the hydraulic retention time of 15 h, the 2-CP removal efficiency reached 92.8% (2-CP decay rate: 0.67 g/m² d of surface area of silicone tube). H₂ was used as electron donor for dechlorinating 2-CP, and produced the dechlorinating intermediate, phenol. Both nitrate and sulfate played important roles in inhibiting 2-CP dechlorination through different biological mechanisms. Nitrate can be easily utilized as an electron acceptor by the biofilm, while sulfate cannot. Results of this study demonstrated that nitrate competed with 2-CP as the electron acceptor, while sulfate retarded the activity of hydrogen-dechlorinating bacteria and thus inhibited the 2-CP dechlorination.     

Diffusion of phenol through a biofilm grown on activated carbon particles in a draft-tube three-phase fluidized-bed bioreactor

Diffusion of phenol through a biofilm attached to activated carbon particles was investigated. The biofilm was grown on activated carbon particles in a draft-tube three-phase fluidized-bed bioreactor operating in a fed-batch mode. It was found that phenol did not adsorb on the biofilm and that the diffusion coefficient of phenol within the biofilm varied from 13 to 39% of its corresponding value in water. The diffusion coefficient of phenol within the biofilm was reduced by increasing the biofilm density. An extensive literature review of diffusion of substrates through biofilms indicated that this conclusion could be extended to biofilms grown on flat surfaces, rotating cylinders, and even bioflocs.     

Biodegradation of phenolic industrial wastewater in a fluidized bed bioreactor with immobilized cells of Pseudomonas putida

The paper presents the main results obtained from the study of the biodegradation of phenolic industrial wastewaters by a pure culture of immobilized cells of Pseudomonas putida ATCC 17484. The experiments were carried out in batch and continuous mode. The maximum degradation capacity and the influence of the adaptation of the microorganism to the substrate were studied in batch mode. Industrial wastewater with a phenol concentration of 1000 mg/l was degraded when the microorganism was adapted to the toxic chemical. The presence in the wastewater of compounds other than phenol was noted and it was found that Pseudomonas putida was able to degrade these compounds. In continuous mode, a fluidized-bed bioreactor was operated and the influence of the organic loading rate on the removal efficiency of phenol was studied. The bioreactor showed phenol degradation efficiencies higher than 90%, even for a phenol loading rate of 0.5 g phenol/ld (corresponding to 0.54 g TOC/ld).     

Membrane-attached biofilms for VOC wastewater treatment. II: Effect of biofilm thickness on performance

This article reports a study of the performance of membrane-attached biofilms grown in a single tube extractive membrane bioreactor (STEMS) used for the treatment of a synthetic wastewater containing a toxic VOC (1,2-dichloroethane [DCE]). Mass balances show that complete mineralization of DCE was achieved, and that the biofilms were effective in reducing air stripping to negligible levels. Experimental results are presented showing the evolution over time of biofilm thickness and its influence on the flux of DCE across the membrane. It has been found that a trade-off exists between the positive influence of biofilms in reducing air-stripping of DCE, and the negative influence of biofilms in reducing DCE flux across the membrane. These considerations lead to an optimal biofilm thickness in the region of 200 to 400 mum being recommended for this system. (c) 1995 John Wiley & Sons, Inc.     

Treatment of phenolics containing synthetic wastewater in an internal loop airlift bioreactor (ILALR) using indigenous mixed strain of Pseudomonas sp. under continuous mode of operation

The scope of this study is to evaluate the performance of internal loop airlift bioreactor (ILALR) in treating synthetic wastewater containing phenol and m-cresol, in single and multi component systems. The microbe utilized in the process was an indigenous mixed strain of Pseudomonas sp. isolated from a wastewater treatment plant. The reactor was operated at both lower and higher hydraulic retention times (HRTs) i.e., 4.1 and 8.3 h, respectively, by providing an inlet feed flow rate of 5 and 10 mL/min. Shock loading experiments were also performed up to a maximum concentration of 800 mg/L for phenol at 8.3 h HRT and 500 mg/L for m-cresol at 4.1 h HRT. The study showed complete degradation of both phenol and m-cresol, when they were degraded individually at a HRT of 8.3 h. Experiments with both phenol and m-cresol present as mixtures were performed based on the 2² full factorial design of experiments.     

Interception of small particles by flocculent structures, sessile ciliates, and the basic layer of a wastewater biofilm

We investigated attachment processes of hydrophobic and hydrophilic particles (diameter = 1 microm) to mature biofilms grown on clay marbles in a sequencing batch biofilm reactor. During a treatment cycle with filtered wastewater containing different fluorescent beads, the progression of particle density in various biofilm compartments (carrier biofilm, basic biofilm layer, biofilm flocs, and sessile ciliates) was determined by flow cytometry, confocal laser scanning microscopy and automated image analysis. Particles were almost completely removed from wastewater by typical processes of particle retention: up to 58% of particles attached to clay marbles, up to 15% were associated with suspended flocs, and up to 10% were ingested by sessile ciliates. Ingestion of particles by ciliates was exceptionally high immediately after wastewater addition (1,200 particles grazer(-1) x h(-1)) and continued until approximately 14% of the water had been cleared by ciliate filter feeding. Most probably, ciliate bioturbation increases particle sorption to the basic biofilm. Backwashing of the reactor detached pieces of biofilm and thus released approximately 50% of the particles into rinsing water. Clay marbles in the upper part of the reactor were more efficiently abraded than in the lower part. No indications for selective attachment of the applied hydrophobic and hydrophilic beads were found. As a consequence of interception patterns, organisms at elevated biofilm structures are probably major profiteers of wastewater particles; among them, ciliates may be of major importance because of their highly active digestive food vacuoles.     

Biofilm development in a membrane-aerated biofilm reactor: effect of flow velocity on performance

The effect of liquid flow velocity on biofilm development in a membrane-aerated biofilm reactor was investigated both by mathematical modeling and by experiment, using Vibrio natriegens as a test organism and acetate as carbon substrate. It was shown that velocity influenced mass transfer in the diffusion boundary layer, the biomass detachment rate from the biofilm, and the maximum biofilm thickness attained. Values of the overall mass transfer coefficient of a tracer through the diffusion boundary layer, the biofilm, and the membrane were shown to be identical during different experiments at the maximum biofilm thickness. Comparison of the results with published values of this parameter in membrane attached biofilms showed a similar trend. Therefore, it was postulated that this result might indicate the mechanism that determines the maximum biofilm thickness in membrane attached biofilms. In a series of experiments, where conditions were set so that the active layer of the membrane attached biofilm was located close to the membrane biofilm interface, it was shown that the most critical effect on process performance was the effect of velocity on biofilm structure. Biofilm thickness and effective diffusivity influenced reaction and diffusion in a complex manner such that the yield of biomass on acetate was highly variable. Consideration of endogenous respiration in the mathematical model was validated by direct experimental measurements of yield coefficients. Good agreement between experimental measurements of acetate and oxygen uptake rates and their prediction by the mathematical model was achieved.     

Biodegradation of saline phenolic wastewater in a biological contact oxidation reactor with immobilized cells of <Emphasis Type="Italic">Oceanimonas</Emphasis> sp.

Objective

To develop a method to treat saline phenolic wastewater in a biological contact oxidation reactor (BCOR) with immobilized cells of a marine microorganism, Oceanimonas sp., isolated from seawater.

Results

Cells were immobilized on fibre carriers in the BCOR. Saline wastewater with phenol at 1.5 g/l and NaCl at 6 % (w/v) was treated. In continuous assays, 99 % removal of phenol was achieved and a kinetic model for the phenol degradation is presented based on Monod’s equation.

Conclusion

The BOCR system using immobilized cells of Oceanimonas efficiently treats saline phenolic wastewaters without having decrease the salinity of the wastewater.

     

Phenol removal in packed bed reactor under denitrifying conditions

Detailed studies on the efficiency of phenol degradation by a biofilm in an anaerobic packed bed reactor were carried out. The efficiency of phenol degradation depended on both the concentration of phenol in the medium and the phenol load in anaerobic packed bed reactor. Increasing phenol concentrations from 200 to 1,250 mg l(-1) and retention time (Tr)= 12 h were paralleled by increasing efficiency of the process, which reached a maximum value of 1,390 mg l(-1) day(-1) at 700 mg phenol l(-1). The highest concentration of phenol used inhibited growth by approximately 95%. When the phenol load in medium containing 200, 300, 400 and 500 mg l(-1) was increased through a shortening of the retention time (Tr from 24 to 2 h) a maximum efficiency of phenol degradation of 2,200 mg l(-1) day(-1) was obtained at Tr=4 h and phenol concentrations in the medium of 200 mg l(-1). Phenol in concentrations from 300 to 500 mg l(-1) was fully degraded at Tr>9 h and phenol load reaching 530-1330 mg l(-1) day(-1) for the individual concentrations. The post-denitrification effluent leaving packed bed reactor in spite of the absence or even trace amounts of phenol in it requires further purification.     

Biodegradation of phenol in synthetic and industrial wastewater by Rhodococcus erythropolis UPV-1 immobilized in an air-stirred reactor with clarifier

Phenol biodegradation by suspended and immobilized cells of Rhodococcus erythropolis UPV-1 was studied in discontinuous and continuous mode under optimum culture conditions. Phenol-acclimated cells were adsorbed on diatomaceous earth, where they grew actively forming a biofilm of short filaments. Immobilization protected cells against phenol and resulted in a remarkable enhancement of their respiratory activity and a shorter lag phase preceding active phenol degradation. Under optimum operation conditions in a laboratory-scale air-stirred reactor, the immobilized cells were able to completely degrade phenol in synthetic wastewater at a volumetric productivity of 11.5 kg phenol m(-3) day(-1). Phenol biodegradation was also tested in two different industrial wastewaters (WW1 and WW2) obtained from local resin manufacturing companies, which contained both phenols and formaldehyde. In this case, after wastewater conditioning (i.e., dilution, pH, nitrogen and phosphorous sources and micronutrient amendments) the immobilized cells were able to completely remove the formaldehyde present in both waters. Moreover, they biodegraded phenols completely at a rate of 0.5 kg phenol m(-3) day(-1) in the case of WW1 and partially (but at concentrations lower than 50 mg l(-1)) at 0.1 and 1.0 kg phenol m(-3) day(-1) in the cases of WW2 and WW1, respectively.     

Anaerobic dechlorination of perchloroethene in an extractive membrane bioreactor

An extractive membrane bioreactor (EMB) is described that used an undefined anaerobic culture to dechlorinate tetrachloroethene (C₂Cl₄) reductively in a synthetic wastewater. Comparable reactors described in the literature use set-ups where the bacteria are in direct contact with the wastewater, and thus would require the addition of significant quantities of nutrients to the wastewater stream in practical application. In the EMB, a silicone rubber membrane separates the microbial culture from the wastewater stream, so that addition of nutrients can be minimised. The EMB was operated continuously for 48 days and dechlorinated 359 mol C₂Cl₄/(l biomedium⁻¹ day⁻¹) on average. Lactate was fed as an electron donor and C₂Cl₄ dechlorination was verified by chloride measurements. Particular attention was paid to the reduction of transmembrane C₂Cl₄ flux caused by a membrane-attached biofilm. Following a start-up period, the reactor operation was stable and remained largely unaffected by biofilm thickness and oxygen contamination from the wastewater. Received: 19 January 1998 / Received revision: 8 May 1998 / Accepted: 8 May 1998