PII: S0043-1354(00)00468-1

Wat. Res. Vol. 35, No. 8, pp. 20032009, 2001 # 2001 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/01/$ - see front matter

ULTRASONIC WASTE ACTIVATED SLUDGE DISINTEGRATION FOR IMPROVING ANAEROBIC STABILIZATION

A. TIEHM1, K. NICKEL, M. ZELLHORN and U. NEIS*
Department of Sanitary and Environmental Engineering, Technical University of Hamburg-Harburg, AB Gewasserreinigungstechnik, Eissendorfer Str. 42, D-21073 Hamburg, Germany (First received 7 March 2000; accepted in revised form 18 September 2000) Abstract}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 dierent ultrasound intensities and treatment times was examined. Sludge disintegration was most signicant 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 eciency 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 oc deagglomeration without the destruction of bacteria cells. Longer sonication brought about the break-up of cell walls, the sludge solids were disintegrated and dissolved organic compounds were released. The anaerobic digestion of waste activated sludge following ultrasonic pretreatment causing microbial cell lysis was signicantly improved. There was an increase in the volatile solids degradation as well as an increase in the biogas production. The increase in digestion eciency was proportional to the degree of sludge disintegration. To a lesser degree the deagglomeration of sludge ocs also augmented the anaerobic volatile solids degradation. # 2001 Elsevier Science Ltd. All rights reserved Key words}anaerobic digestion, sludge stabilization, biogas, ultrasound, cavitation, disintegration

INTRODUCTION

Anaerobic digestion is the most applied technique for sewage sludge stabilization resulting in the reduction of sludge volatile solids and the production of biogas. The anaerobic stabilization is a slow process. Therefore, long residence times in the fermenters and large fermenter volumes are required. Anaerobic degradation of particulate material and macromolecules is considered to follow a sequence of four steps: hydrolysis, acidogenesis, acetogenesis, and methanogenesis. In the case of sewage sludge digestion, the biological hydrolysis has been identied as the ratelimiting step (Eastman and Ferguson, 1981; Shimizu et al., 1993). Therefore, the pretreatment of sewage sludge by mechanical, chemical, or thermal disintegration can improve the subsequent anaerobic digestion (Chiu et al., 1997; Dohanyos et al., 1997; Hiraoka et al., 1984; Mueller et al., 1998). However, there is a lack of information as to how dierent
*Author to whom all correspondence should be addressed. Tel.:+49-40-42878-3107; fax: +49-40-42878-2684; e-mail: neis@tu-harburg.de 1 Present address: Water Technology Center, Karlsruher Str. 84, D-76139 Karlsruhe, Germany.

degrees of sludge disintegration impact on the digestion process. Ultrasonic disintegration is a well-known method for the break-up of microbial cells to extract intracellular material (Harrison, 1991). The impact of ultrasound waves on a liquid causes the periodical compression and rarefaction of the medium. Cavitation occurs above a certain intensity threshold, when gas bubbles are created which rst grow in size before violently collapsing within a few microseconds. The violent collapse produces very powerful hydromechanical shear forces in the bulk liquid surrounding the bubble. It has been shown that macromolecules with a molar mass above 40,000 are disrupted by the hydromechanical shear forces produced by ultrasonic cavitation. The mechanical forces are most eective at frequencies below 100 kHz (Portenlanger, 1999). The temperature and pressure inside the collapsing cavitation bubbles rise up to about 5000 K and several hundred atmospheres. These extreme conditions can lead to the thermal destruction of compounds present in the cavitation bubbles and to the generation of very reactive hydroxyl radicals (Mason, 1991; Young, 1989). In this way sonochemical reactions can degrade volatile pollutants by

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A. Tiehm et al. The degree of disintegration (DDCOD) is calculated as the ratio of COD-increase by sonication to the COD-increase by the chemical disintegration: DDCOD CODUltrasound COD0 =CODNaOH COD0 100% 1 where CODUltrasound is the COD in the supernatant of the sonicated sample (mg l1), COD0 is the COD in the supernatant of the untreated sample (mg l1), CODNaOH is the COD in the supernatant of the reference sample (mg l1). The particle size distribution of sludge samples was determined by the laser light obscuration method based on the time-of-transition principle. A description of the method and the laser instrument (CIS 100; Galai; Israel) was published previously (Neis and Tiehm, 1997). Since repeated measurement of the same sludge sample exhibited signicantly dierent results, ve replicate determinations were done. Results are given as median particle size and standard deviation. The turbidity of sludge samples was measured after centrifugation for 30 min at 40,000 rcf with a nephelometer. Anaerobic sludge stabilization The anaerobic digestion of WAS was studied in ve stirred tank fermenters (Fig. 1) at 378C. Each fermenter had a total volume of 1 l and contained 800 ml of WAS. At the beginning of the digestion experiments, the fermenters were lled with digested sludge from the full-scale Bad Bramstedt digester. The fermenters were operated with 8 days hydraulic sludge retention time in a semi-continuous mode. Three times a week appropriate volumes of WAS were replaced. The produced biogas was collected in calibrated glass cylinders. The cylinders were lled with A. deion. acidied with HCl to pH 0 to avoid losses of CO2 due to the formation of carbonate. The sonication of fresh WAS was done immediately before it was fed to the fermenters. During the fermentation experiments, the concentration of volatile solids (VS), production of biogas and pH were recorded three times a week at each sludge replacement. The aqueous phase COD, NH4-N, and total phosphorus were determined once a week. The concentrations of volatile fatty acids (VFA) and the biogas composition were determined at the end of each experiment. Analytical procedures In order to determine the volatile solids (VS), the samples were rst dried at 1058C for 24 h to obtain the concentration of dry solids. Next, the dry solids were incinerated at 5508C

pyrolytic processes inside the cavitation bubbles and non-volatile pollutants by hydroxyl radical reactions in the bulk liquid (Petrier and Francony, 1997; Tiehm, 1999). While sonochemical degradation processes can occur in a broad ultrasound frequency range from 20 kHz up to about 1 MHz the highest eciency of sonochemical reactions was observed at more than 100 kHz (Hua and Homann, 1997; Petrier and Francony, 1997). Both the hydromechanical shear forces and the sonochemical eects can contribute to the ultrasonic disintegration of sewage sludge. Our previously published studies demonstrated that ultrasonic pretreatment of raw sludge (Tiehm et al., 1997) or waste activated sludge (Neis et al., 1999) allowed for a signicant increase in digester through-put without losses in sludge stabilization. This study was done (i) to obtain more insight into the mechanisms of ultrasonic sludge disintegration, (ii) to study the eect of changing the ultrasound frequency, and (iii) to examine the eect of dierent degrees of sludge disintegration on the anaerobic sludge stabilization process.

MATERIALS AND METHODS

Examination of sludge disintegration Our experiments were done with waste activated sludge (WAS) obtained from the municipal full-scale treatment plant of Bad Bramstedt, Germany. This treatment plant serves about 85,000 P.E. (35% domestic and 65% industrial waste water) and is operated with 16 d sludge age. The oxygen utilization rate (OUR) was measured to assess the overall microbiological activity of WAS. The OUR was determined at 258C after a 5 min aeration of the sludge samples and an addition of acetate as rapidly available substrate (nal concentration 1 g l1 Na-acetate). After stopping the aeration, the decrease of the dissolved oxygen concentration was measured by an electrode, recorded on a plotter, and corrected for oxygen consumption by the electrode itself. The degree of sludge disintegration was assessed by determining the chemical oxygen demand (COD) in the sludge supernatant. A reference (100%) was dened as the aqueous phase COD obtained by chemical sludge disintegration in 0.5 mol l1 sodium hydroxide for 22 h at 208C.

Fig. 1. Experimental setup for anaerobic sludge digestion. The 1 l fermenters were operated semicontinuously with 800 ml waste activated sludge.

Ultrasonic sludge disintegration improves anaerobic stabilization for 2.5 h. The residues after incineration represent the inorganic dry solids. The dierence between the dry solids and the inorganic dry solids represents the volatile solids. For the analysis of aqueous phase supernatants, the particulate sludge material was removed by high-speed centrifugation (30 min at 40,000 rcf ) followed by ltration through 0.45 mm pore size cellulosenitrate membrane lters. The chemical oxygen demand (COD) was determined by oxidation of the organic compounds with K2Cr2O7. The 3+ produced thus was analysed colorimetrically. ReCr agents and equipment were purchased from Dr. Lange GmbH, Dusseldorf, Germany. The concentration of NH4-N was determined after reaction with salicylic acid and hypochlorite. The coloured reaction product was measured colorimetrically at 660 nm. The concentration of total phosphorus in sludge supernatants was determined after acidic hydrolysis of the organic phosphates and poly-phosphates to ortho-phosphate and subsequent reaction of ortho-phosphate with molybdate and ascorbic acid. The resulting blue complex was determined colorimetrically at 600 nm. The biogas composition was determined by a gas chromatograph equipped with a heat conductivity detector. The concentration of the volatile fatty acids (VFA) was determined after acidication of the samples, head space sampling, and determination by a gas chromatograph equipped with a ame ionisation detector (FID). Ultrasound application Sonication was done with an ultrasound reactor equipped with disk transducers (Allied Signal, Kiel, Germany) operating at 41, 207, 360, 616, 1068, and 3217 kHz. The disk transducers (area 25 cm2) were xed at the bottom of the cylindrical reactor (Fig. 2). During sonication, sludge samples were stirred and the temperature was maintained at 25 38C by thermostated jackets. The ultrasonic power input was determined by calorimetric measurement (Mason, 1991). In this study, ultrasonic parameters are used as dened by Hua and Homann (1997):
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Fig. 3. Eect of ultrasound frequency on (a) WAS median particle size and aqueous phase turbidity and (b) degree of sludge disintegration, DDCOD. Error bars represent the standard deviations of ve replicate measurements of the median particle size. Ultrasonic treatment was done for 4 h at 1.8 W cm2.

RESULTS AND DISCUSSION

Ultrasonic sludge disintegration The eect of ultrasound frequency on sludge disintegration was studied in order to nd out the preferential pretreatment conditions. The results of our relevant experiments are presented in Fig. 3(a) and (b). Within the range of explored frequencies between 41 and 3217 kHz, the disintegration of WAS was most eective at the lower end, i.e. 41 kHz. This is demonstrated by the most pronounced reduction of the median sludge particle size as well as the largest increase in turbidity of the sludge samples at low frequency (Fig. 3(a)). Obviously particulate sludge material was broken down into smaller pieces. We also measured the highest degree of disintegration (DDCOD) at 41 kHz (Fig. 3(b)). The signicant increase of the DDCOD was attributed to the breakup of microbial cells leading to the release of intracellular material. The eciency of sludge disintegration decreased with increasing frequency (Fig. 3). Hence we would expect the best disintegration results with the lowest ultrasound frequency of 20 kHz. However such a frequency could not be set with the device available. As we have outlined before, two cavitation phenomena might be responsible for the destruction of solid cell matter: powerful hydromechanical shear forces and sonochemical reactions. Kuttru (1991) described cavitation as a good example of a physical

ultrasonic intensity relates to the power supplied per transducer area, unit (W cm2), ultrasonic density relates to the power supplied per sample volume, unit (W l1), ultrasonic dose relates to the energy supplied per sample volume, unit (Ws l1).

Fig. 2. Sketch of the ultrasound reactor.

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chaos. This becomes even more relevant when dealing with cavitation in an environment like sewage sludge which may be the least suitable example for a well-dened aqueous system. Nevertheless, theoretical considerations are useful to understand the decrease in disintegration ecacy with increasing ultrasound frequency. Cavitation bubble collapse occurs when the expanding bubbles have reached their resonant radius. The resonant cavitation bubble radius is a function of the ultrasound frequency. In pure water, it can be calculated by the following equation (Young, 1989): ro2 R2 r r 3gPo 2

where r is the density of water, or is the resonance angular frequency, Rr is the resonant bubble radius, Po is the pressure exerted on the liquid, and g is the ratio of the specic heats of gases. g correlates to the heat released upon gas compression (Hua and Homann, 1997) and varies from 1.66 to 1.4 and 1.33 for monoatomic, diatomic and triatomic gases, respectively. Equation (2) is valid for pure water and low surface tension. Taking the case of air bubbles in water at atmospheric pressure, the ultrasonic cavitation bubble radius can be approximated as Rr % 3:28fr1 3

Fig. 4. Degree of sludge disintegration (DDCOD) as function of the theoretical resonant cavitation bubble size. The bubble sizes increase with decreasing ultrasound frequency and were calculated for the frequencies applied in the experiments (413217 kHz).

where the resonant bubble radius Rr is expressed in millimetres and fr is the resonance frequency in kilohertz (Young, 1989). The bubble radius is inversely proportional to the ultrasound frequency. The application of low frequencies creates larger cavitation bubbles. Upon bubble collapse, hard mechanical jet streams are produced that are responsible for many cavitation eects observed on solid surfaces. A valid assumption might be that the energy released by a jet stream is a function of the bubble size at the moment of collapse. The number and size of cavitation bubbles in a sludge media may certainly be dierent to a pure water system due to the presence of a high number of solids, dierent density of the liquid, and the presence of dissolved gases. However, the degree of sludge disintegration could be related to the theoretical bubble size calculated by using equation (3). As it appears, starting at a point where R is about 4 mm, the degree of cell disintegration increases proportionally to the logarithm of the bubble radius (Fig. 4). The theoretical approach gives evidence that the hydromechanical shear forces produced by ultrasonic cavitation are more important for sewage sludge disintegration than sonochemical processes. This nding is supported by another study using similar ultrasonic devices. Mark et al. (1998) reported that sonochemical processes, i.e. production of hydroxyl radicals, were most signicant at frequencies between 200 to 1000 kHz but not at 41 kHz.

Fig. 5. Degree of sludge disintegration (DDCOD) as function of the ultrasonic specic energy input. Waste activated sludge samples (dry solids=25.9 g kg1) were sonicated at 41 kHz with dierent ultrasound intensities.

The eect of ultrasound intensity on sludge disintegration was examined at 41 kHz. Interestingly, we could already observe disintegration phenomena at a rather low intensity of 0.1 W cm2. This is well below the cavitation threshold for water which is reported to be about 0.4 W cm2 (Lorimer, 1990). A lower cavitation threshold for sludge seems reasonable due to the presence of a high number of small particles and gas bubbles acting as cavitation nuclei. Figure 5 shows that the degree of sludge disintegration is directly related to the specic energy input expressed as the amount of energy consumed related to the sludge dry solids content. When dealing with sludge disintegration, expressing the energy consumption this way is useful because the sludge dry solids concentration inuences the disintegration eciency (Neis et al., 1999). Since the concentration of dry solids remained constant in our experiments, the same linear correlation would result if the DDCOD had been presented as function of the ultrasonic dose. In this study, the specic energy required to achieve a certain degree of disintegration was higher as compared to a high performance reactor operated with 31 kHz (Neis et al., 1999).

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Taking into consideration the results presented in Figs 3 and 4, the lower operating frequency is expected to be one factor contributing to a higher disintegration eciency. Anaerobic sludge digestion following ultrasonic disintegration The sonication frequency in these experiments was 41 kHz and the sonication time was varied from 7.5 to 150 min in order to obtain dierent degrees of disintegration. At the shortest sonication time (7.5 min) no increase in soluble COD was observed: there was no cell lysis. The oxygen utilization rate of the sample however increased by 10% as compared to the control (Table 1). Thus we observed an improved microbial activity by dispersing the oc agglomerates into smaller units or even single bacteria. When the sonication time was raised to 30, 60, and 150 min, the degrees of disintegration DDCOD were augmented to 4.7, 13.1, and 23.7%, respectively (Table 1). The disintegration pretreatment resulted in a better anaerobic degradation of the WAS. In Fig. 6, this is shown by comparing the volatile solids concentration of the digested sludges (Fig. 6(a)) to the biogas production (Fig. 6(b)) of sonicated and control samples. Table 1 summarizes the results obtained at dierent pretreatment times. The VS reduction of the control fermenter was 21.5%. It was 22.7% in the fermenter operated with the sludge that was sonicated for only 7.5 min causing oc deagglomeration and not cell disintegration. The VS reduction was highest (33.7%) in the digester which was fed with sludge of the highest degree of disintegration. The total biogas production was slightly reduced when the WAS sonicated for only 7.5 min was digested. In the other fermenters fed with disintegrated WAS the biogas production increased sig-

nicantly with an increasing degree of disintegration. The percentage of methane in the biogas also increased with increasing degree of disintegration. Another case where this has been observed is in thermal sludge disintegration (Hiraoka et al., 1984). The specic biogas production, i.e. the biogas production related to the mass of VS degraded, was slightly lower for the disintegrated WAS as compared to the untreated control. This eect might be due to changes in the biochemical fermentation process. Because of the higher methane content in the biogas of the disintegrated WAS, the resulting specic methane production remained almost constant (Table 1).

Fig. 6. Enhanced anaerobic digestion after waste activated sludge disintegration (degree of disintegration DDCOD=23.7%) as demonstrated by (a) a better volatile solids reduction and (b) an increased production of biogas.

Table 1. Eect of ultrasound treatment time on waste activated sludge disintegration and subsequent anaerobic digestion. The applied ultrasonic frequency was 41 kHz Disintegration time (min) Control Disintegration Degree of disintegration DDCOD (%) Oxygen utilization rate (%) Volatile solids degraded (%) Gas production Total biogas (l) Biogas/VS degraded (l kg1) CH4 (%) CH4/VS degraded (l kg1) Digester euent supernatant COD (mg l1) Acetic acid (mg l1) C3C6 VFA (mg l1) NH4-N (mg l1) P total (mg l1)
a

7.5 0.0 110 22.7 2.79 434 63.5 276 202 21 nd 471 19.0

30 4.7 80 27.3 3.39 441 65.9 291 240 9 nd 558 19.3

60 13.1 65 31.4 3.83 433 67.3 291 250 11 nd 560 24.7

150 23.7 23 33.7 4.15 436 68.9 300 622 11 nd 638 20.7

0.0 100 21.5 2.93 483 62.8 303 215 11 nda 516 19.0

nd=not detectable (53 mg l1).

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Table 2. Eect of ultrasound frequency on waste activated sludge disintegration and subsequent anaerobic digestion. At all frequencies, treatment was done with identical ultrasound densities for 60 min Ultrasound frequency (kHz) Control Degree of disintegration DDCOD (%) Volatile solids degraded (%) 0.0 23.5 41 13.9 32.2 207 3.6 28.9 360 3.1 26.3 1068 1.0 25.2

the ordinate in the statistical analysis (10.4%). The positive eect of the oc deagglomeration on the digestion process can be explained by a better availability of single bacteria cells to hydrolysing extracellular enzymes as compared to cells which are embedded and protected in sludge oc agglomerates. The eect of oc deagglomeration on the VS degradation might change with respect to the sludge oc strength and structure (Morgan and Forster, 1992).
Fig. 7. Enhanced volatile solids degradation as function of the degree of sludge disintegration (DDCOD). The sludge retention time in the digesters was 8 days.

CONCLUSIONS

Due to the better biodegradation of disintegrated WAS the concentration of ammonium and phosphorus of the sludge supernatants was higher as compared to the control. There was no direct correlation of the increased ammonium and phosphorus concentrations to the volatile solids degradation since the concentration of dissolved phosphorus especially is strongly aected by precipitation processes like the formation of calcium phosphates. A second set of digestion experiments was done after ultrasound pretreatment with dierent frequencies: 41, 207, 360, and 1068 kHz. As was expected from the preceding experiments, the application of higher frequencies resulted in lower degrees of disintegration and also in lower volatile solids reduction in the digestion process (Table 2). Figure 7 presents a summary of the results of this study and also integrates a value from a pilot-scale digestion experiment with sonicated WAS and the same sludge retention time of 8 days (Neis et al., 1999). The graph shows that anaerobic sludge stabilization is intensied with increasing degrees of disintegration. A regression analysis of the data indicates that the function is linear. The slope of the linear function is 1.9 (Fig. 7). By increasing the degree of disintegration to, say 10%, the anaerobic volatile solids degradation can be improved by 19%. What may seem amazing at a rst glance is the section of the ordinate. As we have shown earlier, short sonication times cause oc deagglomeration but no cell destruction. Our digestion experiments (Table 1) revealed that the VS degradation was slightly improved. The observed increase was 6% which is quite well in agreement with the section of

In this study, ultrasonic disintegration of waste activated sludge was examined in order to improve the anaerobic stabilization process. The most important results are:
*

Ultrasonic sludge disintegration is most eective at low ultrasound frequencies. Hydromechanical shear forces produced by ultrasonic cavitation are predominantly responsible for sludge disintegration. Ultrasonic pretreatment enhances the subsequent anaerobic digestion resulting in a better degradation of volatile solids and an increased production of biogas.

At short ultrasound application times, sludge oc agglomerates are dispersed while no cell destruction occurs. Floc deagglomeration already improves the anaerobic digestion process. At longer treatment times or higher ultrasound intensity, the microbial cell walls are broken and intracellular material is released to the liquid phase. The increase in volatile solids reduction in the anaerobic digester is proportional to the degree of sludge cell disintegration.
Acknowledgements}This study was supported by the German Ministry for Education and Research (BMBF; grant No. 02WS9460/7).

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