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A Study of Sewage Sludge Solubilization by Alkali and Ultrasonic pretreatment
Abstract
In this study, individual(alkaline, ultrasonic) and combined(alkaline+ultrasonic) pretreatment effect on sewage sludge solubilization was investigated. COD solubilization rates increased with the dose of NaOH added: solubilization reached 27.6%. Additional alkaline agents did not increase solubilization further. Ultrasonic pretreatment achieved 33~39% solubilization when 140 W/L amplitude. In(alkaline(pre-treatment)+ultrasonic (after-treatment)) treatment, solubilization increased as the combined intensity in creased(70.4?9.4%). SCOD rising rate(0.076) was achieved.
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The cohesion of activated sludge biological flocs is controlled by the ratio between hydrophilic exopolymers in which bacteria are embedded and hydrophobic interactions. As shown in this study highly hydrophobic bacteria coexist ill the flocs with highly hydrophilic bacteria which seem to release large quantities of exopolymers (polysaccharides, DNA, proteins...). Addition to the activated sludge of easily assimilable nutrients such as glucose does not change the hydrophohicity of bacteria but increases both exopolymer production and the sludge volume index. The environmental conditions aid the bioavailability of nutrients may considerably shift the hydrophilic/hydrophohic balance. Moreover experiments carried out with four different strains to fourteen isolated from activated sludges have shown that a few strains (variable types) have quite considerable possibilities of hydrophobic property variations in the course of growth.
The effect of thermal pretreatment on the characteristics of degradation of waste activated sludge (WAS) in anaerobic digestion was investigated by laboratory-scale batch and continuous experiments at 35 ± 1°C. The pretreatment temperatures of WAS ranged from 62 to 175°C and the pretreatment times were 15, 30, 60, 90 and 120 minutes. The organic particulates in WAS were solubilized to soluble carbohydrates, lipids and proteins or converted into the lower molecular weight compounds, such as volatile fatty acids, by the thermal pretreatment. Through the thermal pretreatment, the anaerobic degradability of WAS and the gas production from WAS were greatly increased, and the retention time necessary for anaerobic digestion was possible to be reduced by 5 days. The optimum pretreatment temperature and pretreatment time for the upgrading of anaerobic digestion of WAS were 170°C and 60 minutes, respectively. At this pretreatment condition, the COD removal and the gas production were markedly increased. At the digester with retention time from 5 to 10 days, the COD removal efficiency reached over 60% and gas production ranged from 223 to 235ml.gCOD-1 which were about 2 times those of the control. The numbers of methanogenic bacteria existing at retention times from 1.5 to 10.0 days ranged from 107 to 108 MPN.ml-1, and reached the maximum population level at the retention time of 5 days. The increase in solubilization and anaerobic degradation of major organic compounds in WAS by thermal pretreatment decreased in the following order: carbohydrates > proteins > lipids.
The slow degradation rate of sewage sludge in anaerobic digesters is due to the rate limiting step of sludge hydrolysis. The effect of ultrasound pretreatment on sludge degradability was investigated using ultrasound at a frequency of 31 kHz and high acoustic intensities. Ultrasound treatment resulted in raw sludge disintegration as was demonstrated by increase of Chemical Oxygen Demand in the sludge supernatant and size reduction of sludge solids. Semi-continuous fermentation experiments with disintegrated and untreated sludge were done for four months on a half-technical scale. One fermenter was operated as a control with a conventional residence time of 22 days. Four fetmenters were operated with disintegrated sludge and residence limes of 22, 16, 12, and 8 days, respectively. In the fermenters operated with identical residence times of 22 days reduction of volatile solids was 45.896 for untreated sludge and 50.3% for disintegrated sludge. The fermentation of disintegrated sludge was stable even at the shortest residence time of 8 days with biogas production 2.2 times that of the control fermenter. Due to ultrasound disintegration a better degradability of raw sludge was achieved that permitted a substantial increase in throughout.
The influence of different pre-treatments was studied in order to observe the effects of temperature, pH and treatment time on Waste Activated Sludge (WAS) solubilization, and anaerobic digestion of pre-treated sludge. Results showed that thermo-chemical pre-treatments were the most efficient on Chemical Oxygen Demand (COD) solubilization, which could reach 83% at 170 °C with pH = 12. Yet, increase in COD solubilization in thermo-chemical pre-treatment was not linked to an increase in soluble Volatile Solids (VS) as optimal conditions were 170 °C, and 130 °C with pH = 10, for this criterion. So, temperature was found to be the most influential parameter on COD and VS solubilization. Biodegradability batch anaerobic tests confirmed results obtained on WAS solubilization, that is to say that 170 °C and 130 °C with pH = 10 were optimal conditions, with respectively 45% and 21% of anaerobic digestion enhancement. Thus these two conditions were chosen for sludge treatment before continuous anaerobic digestion. Results, after stabilization have shown a better efficiency of 170 °C compared with 130 °C with pH = 10 pre-treatment, since after anaerobic digestion it led to 71% of COD degradation and 59% of Total Solids (TS) degradation, with an improvement of 54% in biogas production. The main differences between those two pre-treatments could be due to the pre-treatments themselves more than to an effect on anaerobic digestion, because the first one led to a partial loss of WAS COD (near 17% of initial COD) and the second one to an increase in TS due to addition of base. Copyright © 2004 Society of Chemical Industry
Aerobic and anaerobic digestions were compared in reactors fed with sonicated activated sludge. Sonication treatment of activated sludge led to solubilisation of matter and especially of organic compounds. An important improvement of aerobic and anaerobic biodegradability was observed for a sonication treatment of 108,000 kJ kg TS−1 due to the increase of the instantaneous specific soluble COD uptake rate. Sonication led to an increase of biogas production due to the increase of available soluble COD. In this study, sludge sonication prior to aerobic digestion in the aim of enhancing sludge reduction was inconclusive. Under anaerobic conditions, the enhancement of sludge reduction due to sonication depended on the disintegration degree of the sludge. The combination of high disintegration degree of sonicated sludge prior to an anaerobic digestion led to very good results in term of sludge reduction (80%). Energy balance was also studied.
The influence of sodium hydroxide addition during the thermo-chemical pretreatment of a microbial biomass has been evaluated in terms of particulate chemical oxygen demand (COD) solubilization and anaerobic biodegradability. Both COD solubilization and total solid elimination rates increased with the dose of NaOH added: COD solubilization reached 63%, and total solid elimination was 33% when 5 g Na/l were added. Additional sodium hydroxide addition did not increase COD solubilization further. The observed COD solubilization was due mainly to protein hydrolysis that was directly linked to pH variations. Heating emphasized these pH effects. The higher sodium hydroxide addition (26.1 g/l) led to 85% COD solubilization when heated to 140°C for 30 min instead of 53.2% which was at ambient temperature. Biodegradability and biotoxicity tests were run with pretreated samples. Both methane production and acetate degradation in the presence of pretreated samples were affected as 5 g NaOH/l or more were added. Sodium cation was first suspected to account for the limitations observed. Tests run at pH = 12 with other alkali agents (KOH, Mg(OH)2, or Ca(OH)2), led to the same conclusion: COD solubilization was enhanced but the biodegradability performances were limited. Additional tests run with acetate and increasing NaCl concentrations asserted that sodium cation was not at the origin of the limitations that were attributed to OH− additions: refractory compounds were formed as a consequence of pH modifications.
This study examined how “weak” ultrasonic pre-treatment affects anaerobic digestion of waste biosolids, treated with a cationic polyelectrolyte flocculant. In relation to pre-treatment, the term “weak” used refers to the fact that the total ultrasonic energy input to biosolids is insufficient to fully disrupt its floc structure or the cell walls, as described in the literature. Methane production potential, floc characteristics (size, morphology and ζ-potential) and process parameters (chemical oxygen demands and oxidative-reductive potentials) were monitored, as the digestion was tested. The presence of polyelectrolyte flocculants enhanced methane production within 6 days of digestion (phase I), but inhibited the digestion thereafter (phase II). Following pre-treatment by sonication (0.33 W/mL, 20 min), the methane productions of both original and flocculated biosolids significantly increased. The underlying mechanisms of weak ultrasonic pre-treatment are discussed.
Commonly used pretreatment method of alkaline solubilization (using NaOH) and a relatively new technology of microwave (MW) irradiation (160 degrees C) were combined as a pretreatment method of waste activated sludge (WAS) in this study. First alkaline and MW pretreatment methods were examined separately, then their combination for different conditions was investigated in terms of their effect on COD solubilization, turbidity and capillary suction time (CST). For combined pretreatments, soluble COD to total COD ratio (SCOD/TCOD) of WAS increased from 0.005 (control) to 0.18, 0.27, 0.34 and 0.37 for combined methods of MW and pH-10, 11, 12 and 12.5, respectively. Deteriorated dewaterability due to alkaline pretreatment was also improved due to the incorporation of MW irradiation. Further, with small scale batch anaerobic reactors, pH-10, pH-12, MW (alone), MW+pH-10 and MW+pH-12 pretreated WAS samples were anaerobically digested. Highest total gas and methane productions were achieved with MW+pH-12 pretreatment with 16.3% and 18.9% improvements over control reactor, respectively. Finally the performance of MW+pH-12 pretreatment was examined with 2L anaerobic semi-continuous reactors for 92 days and compared to that of the control reactors. These reactors were operated at an SRT of 15 days. After steady state, 43.5% and 55% improvements were obtained in respective daily total gas and methane productions. TS, VS and TCOD reductions were improved by 24.9%, 35.4% and 30.3%, respectively based on a relative calculation with respect to control reactors. This way combined alkaline-microwave treatment proved to be an effective sludge minimization method. Pretreated digested sludge had 22% improved dewaterability than unpretreated digested sludge. Higher SCOD and NH(3)-N concentrations were measured in the pretreated digested sludge supernatant; however, PO(4)-P concentration did not increase much.
The enzymatic activity of activated sludge was investigated with special emphasis on the localization of the enzymes in the sludge floc matrix. Activated sludge from an advanced activated-sludge treatment plant, performing biological N and P removal, was used. An enzymatic fingerprint was established using a panel of six different enzymes. The fingerprint revealed peptidase as the most dominating specific enzyme tested. By monitoring sludge bulk enzymatic activity over a 3-month period using fluorescein diacetate as an enzyme substrate, considerable variations in activity were observed even over short periods (a few days). The variation in esterase activity was to some extent correlated to the presence of humic compounds in the sludge, but not to the sludge protein content. Comparison of full sludge enzyme activity to the activity of a batch-grown sludge culture indicated that enzymes accumulated in sludge flocs. A large proportion of the exoenzymes were immobilized in the sludge by adsorption in the extracellular polymeric substances (EPS) matrix. This was demonstrated by extraction of EPS from the activated sludge using cation exchange. Contemporary to the release of EPS a very large fraction of the exoenzymes was released into the water. This showed that the exoenzymes should be considered to be an integrated part of the EPS matrix rather than as direct indicators of the microbial activity or biomass.
The pretreatment of waste activated sludge by ultrasonic disintegration was studied in order to improve the anaerobic sludge stabilization. The ultrasound frequency was varied within a range from 41 to 3217 kHz. The impact of different ultrasound intensities and treatment times was examined. Sludge disintegration was most significant at low frequencies. Low-frequency ultrasound creates large cavitation bubbles which upon collapse initiate powerful jet streams exerting strong shear forces in the liquid. The decreasing sludge disintegration efficiency observed at higher frequencies was attributed to smaller cavitation bubbles which do not allow the initiation of such strong shear forces. Short sonication times resulted in sludge floc deagglomeration without the destruction of bacteria cells. Longer sonication brought about the break-up of cell walls, the sludge solids were distintegrated and dissolved organic compounds were released. The anaerobic digestion of waste activated sludge following ultrasonic pretreatment causing microbial cell lysis was significantly improved. There was an increase in the volatile solids degradation as well as an increase in the biogas production. The increase in digestion efficiency was proportional to the degree of sludge disintegration. To a lesser degree the deagglomeration of sludge flocs also augmented the anaerobic volatile solids degradation.
This paper examines the influence of the chemical constituents of activated sludge and extracted extracellular polymeric substances (EPS) on the surface properties, hydrophobicity, surface charge (SC) and flocculating ability (FA) of activated sludge flocs. Activated sludge samples from 7 different full-scale wastewater treatment plants were examined. Protein and humic substances were found to be the dominant polymeric compounds in the activated sludges and the extracted EPS, and they significantly affected the FA and surface properties, hydrophobicity and SC, of the sludge flocs. The polymeric compounds proteins, humic substances and carbohydrates in the sludge flocs and the extracted EPS contributed to the negative SC, but correlated negatively to the hydrophobicity of sludge flocs. The quantity of protein and carbohydrate within the sludge and the extracted EPS was correlated positively to the FA of the sludge flocs, while increased amounts of humic substances resulted in lower FA. In contrast, increased amounts of total extracted EPS had a negative correlation to FA. The results reveal that the quality and quantity of the polymeric compounds within the sludge flocs is more informative, with respect to understanding the mechanisms involved in flocculation, than if only the extracted EPS are considered. This is an important finding as it indicates that extracting EPS may be insufficient to characterise the EPS. This is due to the low extraction efficiency and difficulties involved in the separation of EPS from other organic compounds. Correlations were observed between the surface properties and FA of the sludge flocs. This confirms that the surface properties of the sludge flocs play an important role in the bioflocculation process but that also other interactions like polymer entanglement are important.
This study discovered that biofilm extracellular polymeric substances (EPS) are biodegradable by their own producers and by other microorganisms when they are starved. The study was performed in a comparative fashion to examine the biodegradability of biofilm EPS by the microorganisms from the original biofilm (its own producers) and from activated sludge (other microorganisms). Four distinctive phases were observed during EPS biodegradation. In the first phase, instantaneous concentration increases of carbohydrate and protein in the test solutions were observed when EPS was added; in the second phase, easily biodegradable EPS from the added EPS was quickly utilized; in the third phase, microorganisms began to produce soluble EPS, using the minimally biodegradable EPS left from the previously added EPS; in the fourth phase, cells consumed the newly produced EPS and microbial activity gradually stopped. This study suggests that EPS can be used as a substrate, and that the EPS carbohydrate can be utilized faster than the EPS protein. The EPS utilization rates (including carbohydrate and protein) in the activated sludge suspension were greater than those in the biofilm suspension. It may take microorganisms longer to get acclimated to a new nutrient environment if they are in a starved state.
The purpose of this study was to enhance the efficiency of anaerobic digestion with waste activated sludge (WAS) by batch experiments. We studied the effects of various pretreatment methods (thermal, chemical, ultrasonic and thermochemical pretreatments) on the biogas production and pollutants reduction owing to solubilization enhancement, particle size reduction, increased soluble protein, and increased soluble COD. The thermochemical pretreatment gave the best results, i.e., the production of methane increased by more than 34.3% and soluble COD (SCOD) removal also increased by more than 67.8% over the control. In this case, the biogas production, methane production and the SCOD removal efficiency were about 5037 l biogas/m3 WAS, 3367 l methane/m3 WAS and 61.4%, respectively. Therefore, it is recognized that higher digestion efficiencies of the WAS were obtained through thermochemical pretreatment of the sludge.
The extracellular polymeric substances (EPS) contained in activated sludge flocs resulting from two-sewage treatment plants were extracted according to eight methods referred to in the bibliography. Extracted EPS were characterized by their extraction yield, carbon concentration, their biochemical composition, their HPSEC chromatograms and, where possible, molecular weight (MW) distributions. With HPSEC chromatograms, the use of the mobile phase containing methanol allowed a hydrophobic mechanism for EPS, extracted partly by chemical methods, to be identified. An MW distribution (from 0.1 to 600kDa) was established for EPS extracted by control and physical methods only, from calibration. Except for the resin and heating extraction methods, the EPS extracted from the two sludges displayed the same trend in their HPSEC fingerprints but not in their MW distribution. Results show that the extraction methods using chemical reagents strongly affected the HPSEC fingerprints of EPS, whereas, the physical methods influenced only MW distribution but not HPSEC fingerprints. The use of heat to extract EPS seems to induce hydrolysis of a part of EPS. The HPSEC fingerprint is a good indicator for the appreciation of the consequences of EPS extraction methods on the EPS extracted and the distribution of EPS with low MW in particular.
This study investigated the biodegradability of extracellular polymeric substances (EPS) produced by aerobic granules. Aerobic granules were precultivated with synthetic wastewater in a lab-scale sequencing batch reactor. EPS were extracted from aerobic granules and were then fed as the sole carbon source to their own producers. Results showed that about 50% of EPS produced by aerobic granules could be utilized by their producers under aerobic starvation condition. The average biodegradation rate of the granule EPS in terms of chemical oxygen demand was five times slower than that of acetate, but 50 times faster than that of nonbiodegradable EPS produced by aerobic granules. The nonbiodegradable EPS was mainly found on the outer shell of aerobic granule. EPS produced by aerobic granules basically comprised two major components, i.e., biodegradable and nonbiodegradable EPS. The biodegradable EPS could serve as a useful energy source to sustain the growth of aerobic granules under starvation. This study provides experimental evidence that part of the EPS produced by aerobic granules would be biodegradable, but only nonbiodegradable EPS would play a crucial role in maintaining the structural integrity of aerobic granule.