Bioresource Technology 96 (2005) 16071612

Anaerobic digestion of animal waste: Eect of mixing

Khursheed Karim a, K. Thomas Klasson b, Rebecca Homann a, Sadie R. Drescher b, David W. DePaoli b, M.H. Al-Dahhan a,*
a

Chemical Reaction Engineering Laboratory (CREL), Department of Chemical Engineering, Washington University, 1 Brookings Drive, Campus Box 1198, St Louis, MO 63130 4899, USA b Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA Received 3 March 2004; received in revised form 2 December 2004; accepted 4 December 2004 Available online 26 February 2005

Abstract Six laboratory scale biogas mixed anaerobic digesters were operated to study the eect of biogas recycling rates and draft tube height on their performance. The digesters produced methane at 0.400.45 L per liter of digester volume per day. A higher methane production rate was observed in unmixed digesters, while increased biogas circulation rate reduced methane production. However, dierent draft tube heights caused no dierence in the methane production rate. Air inltration (up to 15% oxygen in the biogas) was observed in the digesters mixed by biogas recirculation. Slight air permeability of tubing or leakage on the vacuum side of the air pump may have caused the observed air inltration. The similar performance of the mixed and unmixed digesters might be the result of the low solids concentration (50 g dry solids per liter of slurry) in the fed animal slurry, which could be suciently mixed by the naturally produced biogas. 2005 Elsevier Ltd. All rights reserved.
Keywords: Anaerobic; Biogas; Draft tube; Digestion; Manure; Mixing

1. Introduction Recent growth of the livestock industries has given rise to new requirements for safe disposal of large quantities of animal waste (manure) generated at dairy, swine, and poultry farms. In the United States approximately 230 million tons of animal waste (dry matter) are generated every year (Sheeld, 2002). Unsafe and improper disposal of decomposable animal waste causes major environmental pollution problems, including surface and groundwater contamination, odors, dust, and ammonia emission. There is also a concern regarding methane emissions, which contribute to the green house eect. Through anaerobic digestion, these large amounts of waste can be converted to methane, a renewable en*

Corresponding author. Tel.: +1 314 935 7187; fax: +1 314 935 7211. E-mail address: muthanna@wuche.wustl.edu (M.H. Al-Dahhan).

ergy source. A survey of dairy and swine farms in the country rearmed that anaerobic digestion is a technology with considerable potential (Lusk, 1998). The survey further suggests that, ignoring caged layer poultry, about 0.426 Tg of methane are potentially recoverable from 3000 dairy and swine farms in 19 states of the USA. Over the past 25 years, anaerobic digestion processes have been applied to a wide array of industrial and agricultural wastes (Speece, 1996; Ghosh, 1997). The performance of anaerobic digesters is aected primarily by the retention time of the substrate in the reactor and the degree of contact between incoming substrate and the viable bacterial population. These parameters are a function of the ow pattern (mixing) inside the reactors. Thorough mixing of the substrate in the digester distributes organisms uniformly and also transfers heat, and thus is regarded as essential in high-rate anaerobic

0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2004.12.021

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Gas bag for gas collection Gas composition sampling

digesters (Sawyer and Grumbling, 1960; Meynell, 1976). Furthermore, agitation helps to reduce particle size as digestion progresses and to release biogas from the mixture. The importance of mixing in achieving ecient substrate conversion has been noted by many researchers (Casey, 1986; Lee et al., 1995; Smith et al., 1996), although the optimum mixing pattern is a subject of much debate. An intermediate degree of mixing appears to be optimal for substrate conversion (Smith et al., 1996). Mixing can be accomplished by mechanical mixers, biogas recirculation, or by slurry recirculation. Mechanical mixers are reported to be most ecient in terms of power consumed per gallon mixed (Brade and Noone, 1981). However, the internal ttings and equipment are not accessible for maintenance during digester operation, and long term reliability of operation is of paramount importance. In general, such reliability can be more readily attained with biogas or liquor recirculation systems, where there are no moving parts within the digester (Casey, 1986). Interestingly, in other literature sources it has been reported that biogas recirculation is the most ecient mode of mixing for anaerobic digesters (Morgan and Neuspiel, 1958; Kontandt and Roediger, 1977; Lee et al., 1995). In the case of a digester mixed with biogas, various parameters which can aect the ow pattern (mixing) inside the digester are: biogas recycling rate, bottom clearance of the draft tube, slope of the hopper bottom, draft tube to tank diameter ratio, position of the biogas injection (sparger) and its design, solids loading rate, among other factors. The current paper evaluates the eects of biogas recycling rates and draft tube heights on the performance of anaerobic digesters mixed with biogas recirculation.

Wet test meter for periodic gas production measurements

Air pump for biogas recirculation Valve for feed

152 mm 344 mm 194 mm 140 mm Draft tube (38 mm dia)

26 mm Valve for effluent

Fig. 1. Schematic diagram of the experimental set-up.

Table 1 Operational conditions for the digesters Digesters Digester Digester Digester Digester Digester Digester 1 2 3 4 5 6 Biogas recirculation rate (L/min) None (unmixed) 1 1 2 3 1 Draft tube height from bottom (mm) 40 40 26 40 40 13

2. Methods 2.1. Experimental design Six laboratory scale digesters (Digesters 16) having a working volume of 3.73 L each were operated at a controlled temperature of 35 2 C. Biogas generated in each digester was collected in a Tedlar bag and was recirculated from the top of the digester by an air pump and draft tube arrangement, as shown in Fig. 1. The digesters were inoculated with 373 mL anaerobic seed sludge collected from a dairy farm operated by the University of Tennessee. The seed sludge had total suspended solids (TSS) of 66.13 g/L and volatile suspended solids (VSS) of 35.63 g/L. The remaining 90% of the working volume was lled with freshly prepared manure slurry having a 5% dry solid concentration (that is, 100 mL of slurry contains 5 g of dry solids). Hydraulic retention time (HRT) was kept constant at 16.2 days,

resulting in a solid loading rate of 3.08 g TS/L-d and an organic loading of 3.37 g TCOD/L-d. Approximately 460 mL of euent was taken from the bottom of the digesters on alternate days and replaced with the same amount of the prepared animal waste slurry. The digesters were operated with four dierent biogas recirculation rates and three dierent draft tube heights described in Table 1. Digesters were operated under steady-state conditions for about three to four weeks. Steady-state conditions were assumed when the coecient of variation for daily biogas production was less than 10% (Vartak et al., 1997). 2.2. Analytical methods Feed and euent samples were analyzed for total solids (TS), volatile solids (VS), TSS, VSS, volatile fatty acids (VFA), total chemical oxygen demand (TCOD), dissolved chemical oxygen demand (DCOD), and total nitrogen (TN). The total volume of the biogas generated was measured, and the composition of the biogas was analyzed three times each week. All the analysis were performed per standard procedures (APHA, 1998) unless otherwise noted.

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Methane Content (%)

60 Gas Composition 50 Gas Production 40 30 20 10 0 11-Oct 0.0 31-Oct 10-Nov 20-Nov 30-Nov 10-Dec 20-Dec Date (2002) 0.5 1.0

2.3. Data analysis Steady-state digester performance data were collected for four dierent biogas recirculation rates and three dierent draft tube positions as described in Table 1. Steady-state conditions were assumed when the coecient of variation for daily biogas production was less than 10%. Average steady-state data and the standard error presented in the paper were calculated as a mean

21-Oct

Fig. 3. Performance characteristics of Digester 2.

Biogas Production (L/L-day)

Volatile fatty acids (formic, acetic, propionic, butyric, and valeric acids) were determined by centrifuging a small sample at 10, 000 rpm for 5 min, ltering the liquid through a 0.2 lm-pore-size lter, and injecting a 10 lL sample into a high pressure liquid chromatograph (HPLC). In the HPLC, the mobile phase (ltered 5 mM H2SO4) was pumped at 0.6 mL/min through a 300 mm 7.8 mm (8 lm particle size) RHM Monosaccharide column (Phenomenex, Torrance, CA) held at a temperature of 65 C to a refractive index detector (Model 2410, Waters Corporation, Milford, MA) held at a temperature of 40 C. Total nitrogen was determined by diluting approximately 1 g of slurry to 50 mL with ultra pure water. Five milliliter of this dilute solution was further diluted with 5 mL of ultra pure water and then digested for 60 min at 121 C, using 1.5 mL potassium persulfate solution (1 g K2S2O8, 1 g NaOH, 17 mL ultra pure water) in Teoncapped vials. Digested samples were cooled and pH was adjusted with H2SO4 (50%) to pH 2.7. This procedure converted all organic and inorganic nitrogen to nitrate, which was measured using a nitrate ion-sensitive electrode (Models 9307, 9300BN, and 900200; Thermo Orion, Beverly, MA) (Smart et al., 1983; Ferree and Shannon, 2001). Biogas volume was measured using wet gas test meters (GSA/Precision Scientic, Chicago, Ill), and 150 lL samples for biogas composition were collected using a gastight syringe. The samples were injected in duplicate into a Hewlett Packard gas chromatograph (Model 5890 Series II, Avondale, PA) gas chromatograph (GC) with a 0.53 mm 30 m GS-Q phase capillary column (J & W Scientic, Folsom, CA). The injector, oven, and thermal conductivity detector (TCD) temperatures were kept as 125, 50, and 250 C, respectively. The carrier gas (helium) ow rate through the column was maintained at 4 mL/min. The samples were injected in a split mode with approximately 10% of the sample going through the column. The column, make-up, and reference gas in the GC was helium. Initially the gas chromatograph was calibrated with separate runs of 99.9% pure methane (CH4), carbon dioxide (CO2), and air injected in volumes between 50 and 200 lL. Later, periodic calibration was performed by injecting dierent amounts of air and using the relationship between TCD response factors described by Dietz (1967).

value over 22 days (i.e., 11 observations). Statistical signicance (P = 0.05) of the experimental data was tested using one way ANOVA and t -test statistical program (Microsoft Excel 2002).

3. Results and discussion Laboratory scale anaerobic digesters were operated to evaluate the eect of dierent biogas recirculation rates and draft tube heights on the methane production rate. As shown in Table 1, Digesters 1, 2, 4, and 5 had the same experimental conditions except for the biogas recirculation rate, while digesters 2, 3, and 6 had the same biogas recirculation rate but dierent draft tube heights. In Figs. 27 the performance characteristics of the six digesters over approximately 60 days are shown. Initially, the biogas production rate varied in all six digesters. This corresponds to a period when a feeding

80 70 60
Methane Content (%)

1.5

Gas Composition 50 40 30 20 10 0 11-Oct Gas Production

1.0

0.5

21-Oct

0.0 31-Oct 10-Nov 20-Nov 30-Nov 10-Dec 20-Dec Date (2002)

Fig. 2. Performance characteristics of Digester 1.

80 70

1.5

Biogas Production (L/L-d)

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K. Karim et al. / Bioresource Technology 96 (2005) 16071612

1.5 80 70
Biogas Production (L/L-d) Biogas Production (L/L-d)

1.5

60
Methane Content (%)

60
Methane Content (%)

Gas Composition 50 40 30 20 10 0 11-Oct Gas Production

1.0

Gas Composition 50 40 30 20 10 Gas Production

1.0

0.5

0.5

21-Oct

0.0 31-Oct 10-Nov 20-Nov 30-Nov 10-Dec 20-Dec Date (2002)

0 11-Oct

21-Oct

31-Oct

0.0 10-Nov 20-Nov 30-Nov 10-Dec 20-Dec Date (2002)

Fig. 4. Performance characteristics of Digester 3.

Fig. 7. Performance characteristics of Digester 6.

80 70

1.5

Gas Composition 50 40 30 20 10 0 11-Oct Gas Production

1.0

0.5

21-Oct

31-Oct

0.0 10-Nov 20-Nov 30-Nov 10-Dec 20-Dec Date (2002)

Fig. 5. Performance characteristics of Digester 4.

80 70 60
Methane Content (%)

1.5

Gas Composition 50 40 30 20 10 0 11-Oct Gas Production

1.0

0.5

21-Oct

0.0 31-Oct 10-Nov 20-Nov 30-Nov 10-Dec 20-Dec Date (2002)

Fig. 6. Performance characteristics of Digester 5.

procedure was changed from three times a week (Monday, Wednesday and Friday) to alternate day feeding. The change in feeding procedure was made to achieve

Biogas Production (L/L-d)

Biogas Production (L/L-d)

60
Methane Content (%)

a HRT of 16.2 days. The biogas production rate was affected during this period, but the methane content of the biogas always remained close to 65%. Gradually the digesters stabilized, and steady-state conditions of less than 10% variation in daily biogas production were achieved in approximately 2830 days. The average steady-state biogas production rate and the methane content are presented in Table 2. Biogas and methane production rates were calculated as the volume of biogas/methane produced per unit volume of digester per day. The digesters produced methane at a rate of 0.400.45 L/L-day (Table 2). The average steady-state data of TS, VS, TSS, VSS, VFA, TCOD, DCOD and TN in the feed and euents from all six reactors are given in Table 3. In all six digesters, TS and VS reductions were about 3038% and 4048%, respectively. Total COD in the feed was approximately 52.7 g/L, 18% of which was present in the form of dissolved COD. The observed reduction of TCOD was 4450% for all six digesters. Volatile fatty acids did not accumulate in any of the digesters. As shown in Table 3, the only fatty acid detected in euent was acetic acid, and the concentration of VFA in euents was very low. The results obtained in the present study were in accordance with the wide range of data reported in the literature. For example, Quasim and Warren (1984) operated a completely mixed mesophilic digester with cattle manure at an organic loading rate of 3.2 kg/m3d and achieved a 52.9% volatile solids conversion to gas. In an another study, Ghaly et al. (1992) observed 40% VS conversion in a completely mixed dairy waste digester at an organic loading rate of 2 kg/m3d. On the other hand, Robbins et al. (1983) observed 30% VS conversion in a completely mixed mesophilic digester operated at an organic loading rate of 2.6 kg/m3d. In order to evaluate the eect of the biogas recirculation rates, the methane production rates of digesters 1, 2, 4, and 5 were plotted as a function of biogas circulation rate, as shown in Fig. 8. The unmixed digester

K. Karim et al. / Bioresource Technology 96 (2005) 16071612 Table 2 Performance data of the digesters Biogas production rate (L/L-d) Digester Digester Digester Digester Digester Digester 1 2 3 4 5 6 0.68 0.027 0.67 0.013 0.69 0.025 0.60 0.023 0.61 0.022 0.65 0.046 Methane content (% CH4) 67 0.1 66 0.2 65 0.6 66 0.3 67 0.6 66 0.3 CH4 Production rate (L/L-d) 0.45 0.019 0.44 0.008 0.45 0.019 0.40 0.016 0.41 0.016 0.44 0.031 H2S (ppm) 350 <2.5 <5 <5 10 <2.5

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O2 Inltration (L/L-d) 0.01 0.03 0.02 0.03 0.02 0.03

Table 3 Average steady-state observation data for feed and euents TS (%) Feed Digester Digester Digester Digester Digester Digester 1 2 3 4 5 6 5.0 3.1 3.5 3.2 3.5 3.3 3.5 VS (%) 2.5 1.3 1.5 1.4 1.6 1.5 1.5 TSS (%) 2.9 2.6 2.6 2.0 3.2 NA NA VSS (%) 1.5 1.2 1.3 0.9 1.5 NA NA VFA (g/L) 3.0 0.06 0.01 0.01 0.03 0.03 0.02 TCOD (g/L) 52.7 26.5 28.2 28.6 29.3 28.8 27.2 DCOD (g/L) 9.45 4.22 3.75 3.83 3.96 4.09 3.95 TN (g/L) 1.33 1.37 1.65 1.37 NA NA NA

NA: Not analyzed.

(Digester 1) produced more methane than the others, and increasing the biogas recirculation rate reduced the methane production rate. The steady-state methane production rate data were subjected to analysis of variance (ANOVA), and a signicant dierence in methane production rates was observed at the 5% level (F = 28.86, df = 3, 40) for the four digesters with dierent biogas recirculation rates. Out of the four digesters, Digester 1 (unmixed) had the highest methane production rate, 0.45 L/L-d. Based on a t-test at the 5% level it is apparent that the Digester 2 (mixed at 1 L/min biogas recirculation rate) produced methane at a rate similar to that of Digester 1 (t = 1.26, df = 40). Based on

0.6

0.5 (0.01) (0.03) (0.03) 0.4 (0.02)

0.3 0 1 2 Gas Circulation Rate (L/min) 3

Fig. 8. Methane production rate for dierent biogas recirculation rates. (Value in parenthesis corresponds to estimated O2 inltration rates in L O2/L-day.)

these results, it can be concluded that increased gas circulation rates reduced the methane production rate. It is important to note that biogas circulation in laboratory digesters increases the chances for inltration of air into the system (due to air permeable tubing, leakage, and other factors) as shown in Table 2. Since the presence of oxygen is known to have a detrimental eect on methane production (Patel et al., 1984), the dierence in the performance of the digesters could be attributed to oxygen inltration. The oxygen inltration was estimated from the nitrogen content in the biogas, which ranged from 3% in digester 1 to 15% in Digester 4, assuming all nitrogen in the biogas was due to air inltration. However, no clear relationship between O2 inltration and methane productivity could be established. One important observation during this study was that slight air inltration into the digesters resulted in the reduction of hydrogen sulde (H2S) in the biogas, as shown in Table 2. Higher methane production rates in unmixed digesters have also been reported by Ghaly and BenHassan (1989). On the other hand Bello-Mendoza and Sharratt (1998) observed that unmixed reactors perform poorly, especially when they were large. The eect of the draft tube heights on the methane production rate of the digesters (Digesters 2, 3 and 6) mixed by biogas recirculation at a rate of 1 L/min is shown in Fig. 9. The digesters performed quite similarly. The steady-state methane production rate data were subjected to analysis of variance (ANOVA) and found to vary insignicantly at the 5% level (F = 1.64, df = 2, 30). Thus, there was no eect of dierent draft tube heights on the methane production rate of the digesters.

CH4 Production (L/L-d)

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K. Karim et al. / Bioresource Technology 96 (2005) 16071612 Dietz, W.A., 1967. Response factors for gas chromatographic Analyses. J. Gas Chromatogr. 5, 6871. Ferree, M.A., Shannon, R.D., 2001. Evaluation of a second derivative UV/Visible spectroscopy technique for nitrate and total nitrogen analysis of wastewater samples. Wat. Res. 35 (1), 327332. Ghaly, A.E., Ben-Hassan, R.M., 1989. Continuous production of biogas from dairy manure using an innovative no-mix reactor. Appl. Biochem. Biotechnol. 20/21, 541559. Ghaly, A.E., Echiegu, E.A., Ben-Hassan, R.M., 1992. Performance of a continuous mix anaerobic reactor operating under diurnally cyclic temperature. In: Presented at the ASAE International Summer Meeting, Charlotte, North Carolina. ASAE Paper No. 92-6025. Ghosh, S., 1997. Anaerobic digestion for renewable energy and environmental restoration. The 8th International Conference on Anaerobic Digestion, Sendai International Center, Sendai, Japan, Ministry of Education, Japan. Kontandt, H.G., Roediger, A.G., 1977. Engineering operation and economics of methane gas production. In: Schlegel, H.G., Barnea, J. (Eds.), Microbial Energy Conversion. Pergamon Press, pp. 379 392. Lee, S.R., Cho, N.K., Maeng, W.J., 1995. Using the pressure of biogas created during anaerobic digestion as the source of mixing power. J. Ferment. Bioengng. 80 (4), 415417. Lusk, P., 1998. Methane recovery from animal manures: A current opportunities casebook. 3rd ed. NREL/SR-580-25145. Golden, CO: National Renewable Energy Laboratory. Work performed by Resource Development Associates, Washington, DC. Meynell, P.-J., 1976. Methane: Planning a Digester. Prism Press, London, 5557. Morgan, P.F., Neuspiel, P.J., 1958. Environmental control of anaerobic digestion with gas diusion. In: McCabe, J., Eckenfelder, W.W. (Eds.), Biological Treatment for Sewage and Industrial Wastes, vol. 2. Reinhold, New York. Patel, G.B., Roth, L.A., Agnew, B.J., 1984. Death rates of obligate anaerobes exposed to oxygen and the eect of media prereduction on cell viability. Can. J. Microbiol. 30, 228235. Quasim, S.R., Warren, K., 1984. Methane gas production from anaerobic digestion of cattle manure. Energy Sources 7 (4), 319 341. Robbins, J.E., Armold, M.T., Weiel, J.E., 1983. Anaerobic digestion of cellulose dairy cattle manure mixture. Agric. Wastes 8, 105118. Sawyer, C.N., Grumbling, A.M., 1960. Fundamental consideration in high-rate digestion. Inc. Sew. Engng. Div. ASCE, 8692. Sheeld, J., 2002. Financial approaches to animal manure management. In: Animal Residuals 2002 Conference and Workshop Report (No: JIEE 2002-04). Smart, M.M., Rada, R.G., Donnermeyer, G.N., 1983. Determination of total nitrogen in sediments and plants using persulfate digestion. Wat. Res. 17 (9), 12071211. Smith, L.C., Elliot, D.J., James, A., 1996. Mixing in upow anaerobic lters and its inuence on performance and scale-up. Wat. Res. 30 (12), 3061. Speece, R.E., 1996. Anaerobic Biotechnology for Industrial Wastewaters. Vanderbilt University, Arachae Press. Vartak, D.R., Engler, C.R., McFarland, M.J., Ricke, S.C., 1997. Attached-lm media performance in psychrophilic anaerobic treatment of dairy cattle wastewater. Biores. Technol. 62 (3), 79 84.

CH4 Production (L/L-d)

0.5 (0.03)

(0.02) (0.03)

0.4

0.3 0 5 10 15 20 25 30 35 40 45 Bottom Position of Draft Tube (mm)

Fig. 9. Methane production for digesters having dierent draft tube heights. (Value in parenthesis corresponds to estimated O2 inltration rates in L O2/L-day.)

4. Conclusions There was no dierence in the performance of all six digesters with dierent mixing conditions. This could be because of the low solids concentration in the fed animal slurry or because of the long HRT of 16.2 days, during which mixing created by the naturally produced gas was sucient for substrate distribution. However, it would be interesting to see if the mixing patterns inside the digesters changed with the applied physical changes in the mixing conditions or not.

Acknowledgements The authors would like to thank the United States Department of Energy for sponsoring the research project (Identication Number: DE-FC36-01GO11054).

References
APHA, 1998. Standard methods for the examination of water and wastewater. 20th ed., American Public Health Association, Washington DC. Bello-Mendoza, R., Sharratt, P.N., 1998. Modeling the eects of imperfect mixing on the performance of anaerobic reactors for sewage sludge treatment. J. Chem. Technol. Biotechnol. 71, 121130. Brade, C.E., Noone, G.P., 1981. Anaerobic digestionneed it be expensive? Wat. Pollut. Control 80, 7076. Casey, T.J., 1986. Requirements and methods for mixing in anaerobic digesters. Anaerobic Digestion of Sewage Sludge and Organic Agricultural Wastes. Elsevier App. Sci. Pub., 90103.