Energy Fuels 2009, 23, 46354639 Published on Web 08/19/2009

: DOI:10.1021/ef900384p

Anaerobic Co-Digestion of Cattle Manure with Corn Stover Pretreated by Sodium Hydroxide for Efficient Biogas Production
Xiujin Li,*, Laiqing Li, Mingxia Zheng, Guozhi Fu, and Jam Saifullah Lar

Department of Environmental Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, P.R. China, and Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, P.R. China Received April 30, 2009. Revised Manuscript Received August 4, 2009

Anaerobic co-digestion of cattle manure with NaOH-treated corn stover for biogas production was investigated. Four cattle manure to corn stover ratios (CM/CS) of 1:1, 1:2, 1:3, and 1:4, and three feeding concentrations (FC) of 50, 65, and 80 g L-1 were used. The results showed that the co-digestion with CM/CS ratio of 1:3 obtained the highest total biogas production of 20.5 L, methane yield of 194 mL CH4 g-1 VS, and TS and VS reductions of 45.0% and 53.0% at the FC of 65 g L-1. Therefore, the FC of 65 g L-1 and CM/CS ratio of 1:3 was selected as the optimal one. Compared to the single digestion, 4.9-7.4% more biogas productions were obtained at the same FC of 65 g L-1 due to the synergistic effect. The synergistic effect is mainly attributed to more balanced nutrients and increased buffering capacity. It indicated that co-digestion of cattle manure with NaOH-treated corn stover could be one of the options for efficient biogas production and waste treatment.

1. Introduction Anaerobic digestion technology can be applied to convert various plant biomass, crop residues, and animal manure into methane-rich biogas, a carbon-neutral source of domestic renewable energy.1 The technology has been given great attention recently for its important role in clean energy production and pollution reduction. So far, over 30 million household-scale small digesters and 3000 large-scale digesters have been built in China. Chinese government has set the goal of building 60 million household-scale digesters in rural areas by 2020.2 Currently, most of digesters use animal manure as feedstock to produce biogas in China. However, manure has limited availability. The shortage of feedstock has become major bottleneck for achieving the goals; therefore, feedstock alternatives need to be developed. On the other hand, China is one of the largest agricultural countries in the world. Approximately, 0.6 billion tons of various crop residues are generated annually.3 Although there are a few methods available for crop residues reutilization, over 50% remains unused.2 Corn is one of the important crops that is widely planted in the northern part of China. It is quite common to see wide fires from open-field burning of corn stover across the corn planting areas during harvest season.4 Serious environmental and safety problems are caused due to the open-field burning of corn stover. On the other hand, Corn stover is one kind of organic material; it has potential to be used as alternative feedstock to produce biogas. If so, it would bring two benefits: (1) to replace partial animal manure and solve the feedstock shortage problem; (2) to provide one
*To whom correspondence should be addressed. E-mail: xjli@mail. buct.edu.cn. Telephone: 86-10-6443-2281. (1) Lehtomaki, A.; Huttunen, S.; Rintala, J. A. Resour., Conserv. Recycl. 2007, 51, 591609. (2) Pang, Y.; Liu, Y.; Li, X.; Wang, K.; Yuan, H. Energy Fuels 2008, 22 (4), 27612766. (3) Wang, J.; Dai, L.; Tian, Y.; Qin, S. Trans. Chin. Soc. Agric. Eng. 2007, 23, 276282. (4) Bian, Y. S. Treatment of Agro-wastes in Eco-agricultural System; Chinese Press of Chemical Industry Beijing: Beijing, 2000; pp 135-139.
r 2009 American Chemical Society

alternative to reuse corn stover and mitigate the pollution associated. However, the biodegradability of corn stover needs to be significantly improved before corn stover can be efficiently used for anaerobic digestion because corn stover contains a high percentage of lignocelluloses, which cannot be effectively digested by anaerobic bacteria and lead to low biogas yield and long digestion time. Pretreatment proved to be one simple but effective method for improving the biodegradability of crop residues. Various pretreatment methods have been investigated by researchers.5-7 Our previous research showed that NaOH pretreatment could significantly improve biodegradability and enhance biogas production of corn stover.2 Our idea was to co-digest animal manure with the NaOH-pretreated corn stover. This could develop new feedstock without affecting biogas production efficiency. Co-digestion of various organic wastes for energy production has attracted increasing interests recently.8 The benefits of co-digestion includes improved biogas yield, economic advantages derived from the sharing of equipment, easier handling of mixed wastes, and synergistic effect.9 According to MataAlvarez et al., digestion of more than one kind of substrate in the same digester could establish positive synergism in the digester; the added nutrients would support microbial growth. Co-digestion of animal manure with various agro-industrial residues has been reported previously,10,11 with particular
(5) Pavlostathis, S. G.; Gossett, J. M. Biotechnol. Bioeng. 1985, 27, 334344. (6) Chen, H.; Liu, L.; Yang, Z; Li, Z. Biomass Bioenergy 2005, 28, 411417. (7) Curreli, N.; Fadda, M. B; Rescigno, A.; Rinaldi, A. C.; Soddu, G..; Sollai, F.; Vaccargiu, S.; Sanjust, E.; Rinaldi, A. Process Biochem. 1997, 32, 665670. (8) Li, R.; Chen, S.; Li, X.; Lar, J. S.; He, Y. Energy Fuels 2009, 23 (4), 22252228. (9) Mata-Alvarez, J.; Mac, S.; Llabrs, P. Bioresour. Technol. 2000, e e 74 (1), 36. (10) Callaghan, F. J.; Wase, D. A. J.; Thayanity, K.; Forster, C. F. Biomass Bioenergy 2002, 22, 7177. (11) Kaparaju, P.; Rintala, J. Resour., Conserv. Recycl. 2005, 43, 175 188.

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: DOI:10.1021/ef900384p
cattle manure 17.1 ( 0.6 84.3 ( 1.2 15.7 ( 1.3 28 ( 2.0 4.8 ( 0.5 6 4.2 ( 0.4 28.1 ( 1.7 17.2 ( 0.6 7.3 ( 0.1 raw corn stover 92.6 ( 1.7 89.7 ( 1.3 10.3 ( 1.3 35.2 ( 2.4 0.6 ( 0.2 59 37.5 ( 0.9 30 ( 2.8 8.4 ( 0.7

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Table 1. Characteristics of Cattle Manure and Corn Stover Used in the Experimentsa
characteristic total solid (TS), wt % volated solid (VS), % dry basis ash, % dry basis C, % dry basis N, % dry basis C/N alkalinity (g CaCO3 L-1) Cellulose, % dry basis hemicellulose, % dry basis lignin, % dry basis
a

NaOH-treated corn stover 90.4 ( 1.4 87.6 ( 1.1 12.4 ( 1.2 33.5 ( 2.2 0.7 ( 0.2 49 36.2 ( 1.6 25.1 ( 1.6 7.5 ( 0.1

Values are means ( SD (n = 3).

interest being shown in the co-digestion of animal manures with straws.1,12-15 However, the straws that they used were raw ones without any pretreatment. This would lead to low biogas yield, limiting their application in large-scale. The objective of this study was to investigate the performance and synergistic effect of co-digestion of cattle manure with NaOH-pretreated corn stover and determine the optimal CM/CS ratio and feeding concentration for efficient bioenergy production. 2. Materials and Methods
2.1. Materials. The cattle manure and corn stover used in this study were collected from Shunyi County of Beijing City, China. The cattle manure was stored in a freezer and kept at the temperature of -20 C for later use. The corn stover was ground into 5-10 mm particles by a hammer mill (FE130, Staida Co., Tianjing, China) after being air-dried. The ground corn stover was pretreated with NaOH. The 2% NaOH, based on dry matter of corn stover, was first dissolved in tap water to make NaOH solution, and then the solution was added into the ground corn stover and mixed completely. The moisture content of the corn stover was adjusted to 88%. The corn stover, with NaOH addition, was then placed in the laboratory at ambient temperature for 3 days. The pretreatment procedures used followed our previous study.16 2.2. Experimental Design. The NaOH-pretreated corn stover was anaerobically digested in the laboratory by batch tests. The total volume of the digester was 2 L each, with an effective volume of 1.0 L. The feeding concentration (FC) of 50, 65, and 80 g L-1 and the CM/CS ratios of 1:0, 1:1, 1:2, 1:3, 1:4, and 0:1 were used. FC was defined as the dry weight of corn stover fed per liter effective volume of digester (g TS L-1). Each digester was seeded with the activated sludge taken from a mesophilic anaerobic digester in Beilangzhong swine farm in Beijing, China. The digester has been stably operated for biogas production for several years. The seeding sludge contained 4.92% total solid (TS), 3.09% volatile solids (VS), and 47.5 g L-1 mixed liquor suspended solids (MLSSs). Each digester was seeded to maintain the activated sludge MLSS in the digester at 15 g L-1, which was based on the research result from Zhang and Zhang.17 The prepared digesters were then placed in shakers (Taicang DHZ-DA, China) operated at mesophilic temperature (35 ( 1 C) and 120 rpm shaking speed. 2.3. Analytical Methods. Biogas volume was monitored every day by the water displacement method, and the corresponding cumulative biogas volume was calculated. The measured
(12) Hills, D. J. Trans. Am. Soc. Agric. Eng. 1980, 23, 15001504. (13) Hashimoto, A. G. Biotechnol. Bioeng. 1983, 25, 185200. (14) Fischer, J. R.; Iannotti, E. L.; Fulhage, C. D. Trans. Am. Soc. Agric. Eng. 1983, 26, 546548. (15) Somayaji, D.; Khanna, S. World J. Microbiol. Biotechnol. 1994, 10, 521523. (16) Zheng, M.; Li, X.; Li, L.; Yang, X.; He, Y. Bioresour. Technol. 2009, 100, 51405145. (17) Zhang, R.; Zhang, Z. Bioresour. Technol. 1999, 68, 235245.

volume was then converted to a volume of gas at standard temperature and pressure (STP) using the ideal gas law, and this volume was then used to calculate the mass of CH4 based on the methane content. The methane content was analyzed every day by a gas chromatograph (GC) (SP-2100, BeiFenRuiLi Co., Beijing) equipped with a molecular sieve (TDX-01) packed 2 m 3 mm stainless-steel column and a thermal conductivity detector (TCD). The temperatures of oven, injector port, and TCD were 120, 150, and 150 C, respectively. Hydrogen was used as the carrier gas at a flow rate of 30 mL min-1. A standard gas (by BeiFenRuiLi Co., Beijing), consisting of 5.0% N2, 60.1% CH4, and 34.9% CO2, was used for the calibration of the system. TS, VS, MLSS, pH, and alkalinity were measured according to the APHA standard methods.18 The contents of lignin, cellulose, and hemicellulose were determined according to the procedures proposed by Van Soest et al.19 The total carbon (TC) and total nitrogen (TN) were determined by the TC analyzer (Skalar Primacsslc, The Netherlands) and the total Kjeldahl nitrogen analyzer (Model KDN-2C, Shanghai).

3. Results and Discussion 3.1. Feedstock Characteristics. The characteristics of cattle manure and corn stover are shown in Table 1. Compared to the untreated one, the lignin content of NaOH-treated corn stover was decreased from 8.4% to 7.5%, which was beneficial for the release of cellulose and hemicellulose and increasing the accessibility of the microorganism. The cellulose and hemicellulose content of corn stover was about 61.3%, which was 35.3% higher than the cattle manure. The cellulose and hemicellulose were the main carbon source for anaerobic microorganism. The C/N ratio of cattle manure was 6, which was too low to meet the nutrients balance requirement of anaerobic microorganism, while the corn stover had a higher C/N ratio (59). The proper C/N ratio for anaerobic digestion is 25-35.17 The co-digestion of cattle manure with corn stover could provide a more appropriate C/N ratio and more balanced nutrients. In addition, the alkalinity of cattle manure was 4.2 g CaCO3 L-1; it could increase the buffering capacity of the digesters and prevent the acidification occurrence during digestion. 3.2. Co-Digestion Performances. Four co-digestion CM/ CS ratios of 1:1, 1:2, 1:3, and 1:4 were used, and each CM/ SM ratio was tested at three feeding concentrations of 50, 65, and 80 g L-1. The daily biogas production for each codigestion test is shown in Figure 1. Similar trends of daily biogas production were observed for all co-digestion tests. The biogas production started after seeding, kept increasing
(18) APHA. Standard Methods for the Examination of Water and Wastewater, 20th ed.; American Public Health Association: Washington, DC, 1998. (19) Van Soest, P. J.; Robertson, J. B.; Lewis, B. A. J. Dairy Sci. 1991, 74, 35833597.

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Figure 2. Total biogas production of co-digestion of cattle manure with corn stover.

Figure 3. Comparisons of biogas yields. Figure 1. Daily biogas production of co-digestion.

until reaching the first peak, and then began to decline. Several peaks appeared as the digestion process proceeded. The main differences were the peak values of daily biogas production and lasting time of biogas production. Generally speaking, the biogas started generating earlier but shorter time for the lower FC, while generated later but lasted for a longer time for the higher FC. This could be explained by the fact that higher FC means more substrate applied, thus taking a longer time for the anaerobic microorganisms to digest. The co-digestions with CM/CS ratios of 1:3 and 1:4 at the FC of 80 g L-1 showed apparent acidification phenomena at an early stage but recovered two weeks later. This should be attributed to the improved buffering capacity of co-digestion. The total biogas productions (TBPs) for different codigestion tests are shown in Figure 2. For four CM/CS ratios of 1:1, 1:2, 1:3, and 1:4, the co-digestions with the FC of 65 g L-1 obtained TBPs of 19.8-20.5 L, which were 34.8-42.3% and 9.0-113.5% higher than the co-digestions with the FC of 50 and 80 g L-1, respectively. The lower TBPs with the FC of 50 g L-1 should be attributed to less substrate available to anaerobic bacteria. However, the lower TBPs with the FC of 80 g L-1 were mainly due to the acidification that occurred at the early stage of anaerobic digestion. Among the four ratios, the co-digestion with CM/CS ratio of 1:3 achieved highest TBP of 20.5 L at the FC of 65 g L-1. To further compare the biodegradability improvement, biogas yield, which was defined as biogas production per unit volatile solids feed (B/VS), was advanced (Figure 3). For four
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Figure 4. Total methane production of co-digestion of cattle manure with corn stover.

CM/CS ratios, the co-digestions with the FC of 50 g L-1 and 65 g L-1 achieved 306-340 mL g-1VS and 325-356 mL g-1 VS biogas yields, respectively, which were obviously higher than the FC of 80 g L-1. The co-digestion with a CM/CS ratio of 1:3 and FC of 65 g L-1 obtained the highest biogas yield of 356 mL g-1 VS. This indicated that this CM/CS ratio might provide more balanced nutrients and buffering capacity and thus enhance the anaerobic process and bioenergy production. The energy contained in biogas is determined by both biogas volume and methane content. The methane contents for all corn stovers were measured during the whole digestion period of time. The total methane productions (TMP) for each feedstock was calculated by summing daily methane production, which was calculated by timing daily biogas

Energy Fuels 2009, 23, 46354639

: DOI:10.1021/ef900384p

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production with corresponding methane content. The results are presented in Figure 4. It can be seen that the TMP of the reactors fed with 65 g L-1 was significantly higher than the others. At the FC of 65 g L-1, the TMPs were 9.6-11.1 L for the four reactors with the manure to corn stover ratio of 1:1, 1:2, 1:3, and 1:4, respectively. The methane yield was defined as methane production per unit VS feed (CH4/VS). It was observed that the co-digestion with the FC of 65 g L-1 and CM/CS ratio of 1:3 achieved the highest methane yield of 194 mL CH4 g-1 VS (Figure 5). The result conformed to the TBP result as mentioned above. Therefore, the FC of 65 g L-1 and a CM/CS ratio of 1:3 were selected as the optimal ones. Hashimoto13 reported that the methane yield

Figure 5. Comparisons of methane yields.

Figure 6. Comparisons of TS and VS reductions.

of co-digestion of cow manure and wheat straw at the ratio of 1:3 was 70 mL CH4 g-1 VS, which was much lower than the results in this study. The difference is that the researcher employed raw stalks without NaOH pretreatment as done in this study; therefore, the synergistic effect scale was different. Biogas is generated from the biological conversion of substrate. The amount of dry matter of substrate and organic compounds, which are represented by TS and VS, will be reduced. There are close relationships between biogas yield and TS and VS reductions. Therefore, TS and VS reductions were calculated. The results are shown in Figure 6. It can be seen that with the FCs of 50 and 65 g L-1, the reactors with the manure to corn stover ratio of 1:3 and 1:4 obtained higher TS and VS reduction as compared to the other two ratios. TS reductions for the reactors with the manure to corn stover ratio of 1:3 and 1:4 at 50 g L-1 were 53.1% and 52.1%, respectively; the corresponding VS reductions were 57.8% and 58.3%, respectively. TS reductions for the reactors with the manure to corn stover ratio of 1:3 and 1:4 at 65 g L-1 were 45.0% and 49.7%, respectively; the corresponding VS reductions were 53.0% and 56.2%, respectively. The results imply that the biodegradability was improved by adding corn stover into cattle manure from the manure to corn stover ratio 1:1 to 1:4. The increased TS and VS reductions could explain why biogas yields of the reactors with the manure to corn stover ratios at 50 and 65 g L-1 were more than others. 3.3. Synergistic Effect Analysis. One of the important benefits of co-digestion is synergistic effect. The co-digestions with four CM/CS ratios at the FC of 65 g L-1 achieved higher biogas yield and methane yield. Thus, they were selected for synergistic effect analyses. The biogas productions for the co-digestions with CM/CS ratios of 1:1, 1:2, 1:3, and 1:4 were obtained directly from experiments. The biogas productions for manure fraction and stover fraction in codigestions were calculated in terms of the biogas productions of single-digestions with manure alone (1:0) and stover alone (0:1), respectively. The experimental and calculating results are shown in Table 2. It was found that compared to the single-digestions at four CM/CS ratios, the co-digestions achieved 4.9-7.4% more biogas production. The differences were significant (p < 0.05). This means that based on the same amount of manure and stover feedstock, more bioenergy can be generated when the co-digestion process is applied. The increase in biogas production is considered to be from the synergetic effect in the co-digestion process. Mata-Alvarez et al.9 stated that digestion of more than one kind of substrate could establish positive synergism in the digester. Other researchers12-14 also found synergistic effects in co-digestion of other materials and animal manures. Li et al.8 found that the co-digestion of kitchen waste and cattle manure increased methane yield by 44% as compared to the single digestion of kitchen waste, and the increase

Table 2. Synergistic Effect of Co-Digestion of Cattle Manure with Corn Stover at a Feeding Concentration of 65 g L-1
biogas production (mL) total dry matter (g) CM/CS ratio dry matter of manure (g) dry matter of stover (g) co-dige-stion single manure single stover increase (%) 65 65 65 65 65 65 1:0 1:1 1:2 1:3 1:4 0:1 65 32.5 21.7 16.3 13 0 0 32.5 43.3 48.8 52 65 18390 ( 380 19790 ( 750 20450 ( 500 20280 ( 330 14430 ( 135 7215 ( 65 4817 ( 70 3619 ( 110 2886 ( 40 0 0 10275 ( 275 13689 ( 910 15428 ( 130 16440 ( 190 20550 ( 225 5.1 ( 0.1 6.9 ( 1.6 7.4 ( 1.3 4.9 ( 0.5

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could be attributed to the synergistic effect of the increased alkalinity and buffering capacity and the structural changes of cattle manure fibers in the co-digestion process. The synergistic effect is mainly attributed to more balanced nutrients and increased buffering capacity in co-digestion. More balanced nutrients in co-digestion would support microbial growth for efficient digestion, while increased buffering capacity would help maintain the stability of the anaerobic digestion system. 4. Conclusions Anaerobic co-digestion of cattle manure with NaOH-treated corn stover could enhance biogas production and obtain stable performances of anaerobic digestion. The co-digestion with the FC of 65 g L-1 and CM/CS ratio of 1:3 achieved the highest biogas production, methane yield, and TS and VS reductions, which were 20.5 L and 194 mL CH4 g-1 VS and

45.0% and 53.0%, respectively. Therefore, the FC of 65 g L-1 and CM/CS ratio of 1:3 were selected as the optimal ones. Compared to single-digestion, 4.9-7.4% more biogas productions were obtained at the FC of 65 g L-1 due to the synergistic effect. The synergistic effect is mainly attributed to more balanced nutrients and increased buffering capacity. The results showed that co-digestion of cattle manure with NaOH-treated corn stover could be one of the options for efficient biogas production and waste treatment. Further research needs to be conducted on how nutrient balance is improved in co-digestion and how synergestic effect impacts biogas production in continuous feeding digesters.
Acknowledgment. The authors are grateful for the financial support from National Hi-tech R&D Program of China (2006AA10Z425) and National Key Technologies R&D Program of China (2008BADC4B13).

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